Ag2O/Bi2O2CO3 p-n heterojunctions are prepared with commercial Bi2O2CO3 as precursor via a simple photosynthesis process. The obtained Ag2O/Bi2O2CO3 p-n heterojunctions show higher photocatalytic activity than that of pure n-Bi2O2CO3, and the obtained Ag2O/Bi2O2CO3 (AB-4) heterojunction exhibits the best photocatalytic activity under visible light (λ > 400 nm), with which Rhodamine B, methyl blue and methyl orange can be completely degraded within 12 min. Photoluminescent spectra and photoelectrochemical measurement further indicate that the Ag2O/Bi2O2CO3 p-n heterojunctions greatly enhance the charge generation and suppress the charge recombination of photogenerated electron-hole pairs, which would be beneficial to improve their photocatalytic activity.