The novel visible-light-responsive direct solid-state Z-scheme g-C3N4/BiOI heterojunction has been synthesized successfully by means of a solid phase calcination method and used for the degradation of microcystin-LR (MC-LR). The layered g-C3N4 disperses on the surface of BiOI microspheres. The samples are characterized by FESEM, HRTEM, XRD, FT-IR, UV-vis spectroscopy, XPS, BET, PL, and Mott–Sckottky. The photocatalytic activity and photodegradation mechanism of the as-prepared g-C3N4/BiOI microsphere photocatalysts are conducted under visible light irradiation using MC-LR as the target pollutant. The g-C3N4/BiOI material exhibits superior photocatalytic performance when compared with pure BiOI, the possible reason is the efficient separation of photogenerated carriers at the interface between g-C3N4 and BiOI. The heterostructure is responsible for the improved separation efficiency of photogenerated electron–hole pairs and thus the higher photocatalytic activity. The possible photocatalytic mechanism is proposed based on relative band positions of these two semiconductors.