Archbishop Timothy Costelloe, writing in Catholic newspaper The Record, said governments did not have the right to "dismantle" the institution of marriage because they had not created it.
"Marriage is perhaps the oldest human institution we know of," he said. "It certainly pre-existed modern Australia and its parliamentary system and, indeed, pre-existed all parliaments. This essential link between marriage and the family, and the right of children to be raised by their mother and father in a loving and stable family, are the basis for the state's role in regulating marriage."
Archbishop Costelloe, who succeeded Barry Hickey this year, had previously refused to be drawn publicly into the same-sex marriage debate.
Archbishop Costelloe also took aim at critics of same-sex marriage opponents, saying accusations of homophobia were unfair because they were premised on the idea marriage should be open to anyone, which he said was wrong.