Exploring noble-metal-free co-catalysts highly flexible for separating the photogenerated charge carriers is of prime importance for the visible-light-driven photocatalysis. Herein, three-dimensional flower-like BiOI microspheres were fabricated and applied to support noble-metal-free LaCoO3 co-catalysts to construct a unique LaCoO3/BiOI hybrid photocatalyst with a higher ability in charge separation. As expected, the optimum tetracycline degradation rate of LaCoO3 (4.0 wt%)/BiOI was up to 0.0161 min(-1), which was nearly 3.4 fold larger than that of pure BiOI (0.0048 min(-1)). The enhanced photocatalytic performance was mainly ascribed to the vital role of LaCoO3 co-catalyst, which acted as an excellent electron collector for capturing the electrons generated by BiOI, effectively promoting the separation of photogenerated charge carriers and prolonging the lifetime of photo-induced electron-hole pairs at the same time. Furthermore, the active species trapping experiments revealed that the excellent photocatalytic activity was primarily driven by photogenerated holes and superoxide radicals. This work is expected to provide a new inspiration for rationally designing and fabricating noble-metal-free co-catalyst system with high efficiency applied in environment purification.