The visit follows the announcement from five Church of England bishops of their decision to join the Roman Catholic Church.
Dr Williams, the spiritual leader of Anglicans worldwide, will visit the Vatican on November 17 in honour of the 50th anniversary of the Pontifical Council for the Promotion of Christian Unity.
The council aims, in part, to develop dialogue and collaboration with other churches and world communions.
Metropolitan John Zizioulas of Ecumenical Patriarchate of Constantinople and the Archbishop Kurt Koch, president of the council, will also attend.
Earlier this week, it was confirmed that five bishops would defect from the Anglican Communion to the Catholic Church. On Monday, Williams accepted "with regret" the decision of the Anglo-Catholic bishops who are leaving over the consecration of women bishops.
The bishops issued a statement explaining their reasons for leaving the Church of England: "[P]articularly we have been distressed by developments in Faith and Order in Anglicanism which we believe to be incompatible with the historic vocation of Anglicanism and the tradition of the Church for nearly two thousand years."
They said they would resign from their pastoral responsibilities on December 31 and join an ordinariate once one is created by the Roman Catholic Church.
The Vatican has welcomed the defected bishops, two of whom are retired.
Last year, the Vatican made a historic decision to create an apostolic constitution that would provide Vatican guidelines on integrating disaffected Anglicans into the Roman Catholic Church. Pope Benedict XVI made the provision in response to the numerous requests he received from Anglicans unhappy with the ordination of women and noncelibate gay bishops.
More details on the ordinariate will be announced following a meeting among Catholic cardinals on November 19. The Catholic Bishops’ Conference of England and Wales said in statement that it would explore the establishment of the ordinariate and the "warm welcome we will be extending to those who seek to be part of it".
The structure would allow converts to enter into full communion with Rome but still retain certain Anglican rituals and traditions. For example, married clerics would be able to become Catholic priests but not Catholic bishops.
One of the breakaway bishops, John Broadhurst, the Bishop of Fulham, predicts that an exodus of "thousands" of lay Anglicans will occur once the ordinariate is formed.
"There are lots of people interested. Some are actively looking at it," Bishop Broadhurst told The Australian.