Is my friend's theory that God created more than one set of first parents heretical?
The short answer
The theory is polygenism, and Pius XII taught in Humani Generis that the faithful cannot embrace it, since it is not apparent how it could be reconciled with original sin coming from one individual, Adam. As for Cain's wife, Adam and Eve had other children, including daughters.
Pius XII
In Humani Generis (37), Pius XII taught that the faithful cannot hold that after Adam there were true human beings not descended from him, or that "Adam" represents a number of first parents. It is not apparent how this could be reconciled with the Church's teaching that original sin comes from a sin committed by an individual Adam and is passed on to all by generation.
Cain's wife
Scripture doesn't record their names, but Adam and Eve had other children, including daughters, and Cain seems to have married a sister. This was necessary for a time to propagate the human race, as St. Augustine explains in The City of God (book XV); when the necessity ended, so did God's allowance.
Continue exploring
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