The decision to expel former archbishop Francisco Jose Cox Huneeus and former bishop Marco Antonio Ordenes Fernandez -- the latest heads to roll in a country hit hard by the cleric abuse scandal -- is not open to appeal.
Both were stripped of their priesthood "as a consequence of overt acts of abuse against minors", it said.
Saturday's defrocking was "an extremely unusual, if not unprecedented" move, wrote Ines San Martin, a Vatican expert working for specialist Catholic website Crux.
Defrocking is considered the Church's harshest penalty for priests, barring the offender from exercising any clerical duties at all, even in private. Scores of new cases involving the abuse of minors by priests have come to light in Chile, deepening a crisis in the Roman Catholic Church that has also embroiled Pope Francis.
They discussed "the painful scourge of abuse of minors, reiterating the effort of all in collaboration to combat and prevent the perpetration of such crimes and their concealment", the Vatican said.
The leaders "shared the hope that the church could live a true rebirth," Pinera said in a statement.
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