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When Milan was the capital of the west, it surpassed Rome in importance because the imperial court was there. Christianity was made the state religion of the empire with the Edict of Milan. Two fathers of the Catholic church worked in Milan.
When Constantine, the first Christian emperor, began building churches in Rome, the local Christians had a small shrine on Vatican hill where they claimed St Peter was buried. Constantine had the first St Peter's Basilica built on that particular site.