During a mass to mark the three-week meeting of Roman Catholic bishops, the pope delivered a homily on "solitude, love between man and woman, and the family".
He referred to Genesis, the first book of the Bible, as a bedrock for understanding human relationships.
"This is God's dream for his beloved creation: to see it fulfilled in the loving union between a man and a woman, rejoicing in their shared journey, fruitful in their mutual gift of self," he said.
The synod is the second and final round of a review of Catholic teaching on the family.
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But the gathering of 360 participants has been overshadowed by a bombshell announcement by a Polish priest, Krzystof Charamsa, who works for the Vatican body that enforces Catholic dogma, the Congregation for the Doctrine of the Faith.
In separate interviews to Italy's Corriere della Sera and the Polish edition of Newsweek on the eve of the synod, Charamsa, 43, announced he was a practising homosexual with a partner.
"I know that the Church will see me as someone who did not know how to fulfil his duty (to remain chaste), who is lost and who is not even with a woman but with a man!"
Charamsa said his decision to come out was motivated by concern for the Church's attitude to homosexuals, which he described as "backwards".
He presented a 10-point "liberation manifesto" against "institutionalised homophobia in the Church", which he said particularly oppressed the gay men who, according to him, make up the majority of priests.
Charamsa will be unable to continue in his present job and his local bishop will determine "the other aspects of his situation", it warned.
Homosexuality is just one of a wide range of topics to be discussed at the synod, and some prelates have called for it not be included in the programme, according to Church sources.