Speaking in Latin on the steps of St. Peter's Basilica, Benedict solemnly read out the names of the six new saints, declaring each one worthy of veneration in all the Catholic Church.
"Let us be drawn by these shining examples, let us be guided by their teachings," Benedict said in his homily, delivered in English, French, Italian, Polish and Spanish to reflect the languages spoken by the church's newest saints.
A cheer had broken out in the crowd when Mary MacKillop's name was announced earlier in the Mass, evidence of the significant turnout of flag-toting Australians celebrating the humble nun who was briefly excommunicated in part because her religious order exposed a pedophile priest.
Even more MacKillop admirers- an estimated 10,000 - converged Sunday at the Sydney chapel where she is buried and at Sydney's Catholic cathedral, where a wooden cross made from floorboards taken from the first school that MacKillop established was placed on the steps.
Thousands of others in Australia spent their Sunday evenings watching live broadcasts of the Vatican ceremony on television in homes and on large outdoor screens in Sydney, in Melbourne where she was born, as well as in Penola where she established her first school.
Born in 1842, MacKillop grew up in poverty as the first of eight children of Scottish immigrants. She moved to the sleepy farming town of Penola in southern Australia to become a teacher, inviting the poor and the Aborigines of the area to attend free classes in a six-room stable.
She co-founded her order, the Congregation of the Sisters of St. Joseph of the Sacred Heart, with the goal of serving the poor, the sick and the disadvantaged, particularly through education.
"She supported Aboriginal people because she believed in supporting people who were disadvantaged," said Melissa Brickell, a pilgrim from Melbourne who was in St. Peter's Square on Sunday for the ceremony. "She is a friend of Aboriginal people from the early days."
As a young nun, MacKillop and 47 other nuns from her order were briefly dismissed from the Roman Catholic Church in a clash with high clergy in 1871. In addition to bitter rivalries among priests, one of the catalysts for the move was that her order had exposed a pedophile priest.
Five months later, the bishop revoked his ruling from his deathbed, restoring MacKillop to her order and paving the way for her decades of work educating the poor across Australia and New Zealand.
In his homily, Benedict praised MacKillop for her "courageous and saintly example of zeal, perseverence and prayer."
"She dedicated herself as a young woman to the education of the poor in the difficult and demanding terrain of rural Australia, inspiring other women to join her in the first women's community of religious sisters of that country," Benedict said in English.
MacKillop became eligible for sainthood after the Vatican approved a second miracle attributed to her intercession, that of Kathleen Evans, who was cured of lung and brain cancer in 1993.
In a statement Sunday, Evans said she was humbled by MacKillop's example, grateful for her healing and overjoyed that MacKillop's example will now be known to others.
"I think she would be delighted to see so many people looking at their own lives and considering how they can live better and care more," said Evans, who brought relics of MacKillop up to the altar during the canonization Mass.
Veronica Hopson, 72, was MacKillop's first miracle, cured of leukemia in 1961. She broke half a century of silence about her case, telling Australia's Channel Seven's Sunday Night program: "How does a miracle feel? I feel very fortunate that I was given the opportunity to live my life, have a family, have grandchildren, so that's a miracle."
Hopson was 22 when she was diagnosed with leukemia and given only weeks to live. She said her mother contacted nuns at Saint Joseph's convent in northern Sydney where Hopson was taught as a schoolgirl and where MacKillop once lived. The nuns brought cloth that MacKillop had worn and prayed for Hopson.
Hopson, who has had six children and four grandchildren and is recovering from recent bowel cancer, said her miracle also carried a message for people who did not believe in God.
"I guess they must have some sort of hope, not just give in and just let the illness or sad things that happen in their life take over their life. Just keep hoping that it will get better," she said.
Quebec's flag was also out in force in St. Peter's Square in support of Brother Andre Bessette, a Canadian brother who legend says healed thousands of sick who prayed with him at his Montreal oratory.
Born in 1845, Brother Andre was orphaned at the age of 12. After taking his religious vows, he devoted his life to helping others and gained a reputation as a healer. When he died in 1937 at the age of 91, an estimated 1 million people came to pay homage.
"Doorman at the Notre Dame College in Montreal, he showed boundless charity and did everything possible to soothe the despair of those who confided in him," Benedict said in French.
"I think all the people from Quebec are happy now," said Alain Pilote, a 49-year-old pilgrim from Rougemont, near Montreal, who came to Rome for the Mass.
Australia's foreign minister, Kevin Rudd, was in Rome for the canonization as was Canada's foreign minister, Lawrence Cannon. The Polish president, Bronislaw Komorowski, joined thousands of Polish pilgrims to honor that country's latest saint, Stanislaw Kazimiercyzk.
Also being canonized Sunday were Italian nuns Giulia Salzano and Battista Camilla da Varano, and Candida Maria de Jesus Cipitria y Barriola of Spain.
Associated Press reporters Rod McGuirk in Canberra, Australia, and Gianfranco Stara in Rome contributed to this report.