The Fourteenth Ordinary General Assembly of the Synod of Bishops is set to take place from October 4 through to October 25 and will look at the role of the family in the church and the world.
The bishop of Tonga, Cardinal Soane Patita Mafi, and the Archbishop of Suva, Peter Loy Chong, will join the bishop of Kundiawa, Anton Bal, who will represent Papua New Guinea and Solomon Islands.
Cardinal John Dew, of Wellington, will also travel to the Vatican.
He and Cardinal Mafi were appointed cardinals by Pope Francis earlier this year and were also appointed as prelates to the synod.
The Communications advisor to New Zealand Catholic Bishops, Simone Olsen, said its important for isolated geographic regions to be represented.
More than 360 participants, including 18 married couples from around the world are expected to attend.