Although the heterogeneous activation of periodate (PI) has recently garnered significant attention for organic pollutant degradation, regulating the non-radical and radical reaction pathways remains a challenge. Herein, a Z-scheme Fe3O4/g-C3N4 heterojunction (FCN) was developed to achieve controllable radical and non-radical PI activation using a light switch. In the dark, the interaction between FCN and PI gave rise to metastable surface-activated PI complexes (PI*) via the non-radical pathway, which served as the dominant reactive species for organic elimination. Upon light irradiation, FCN acted as an electron donor for PI activation via the radical pathway, forming iodate radicals (IO3•) for pollutant destruction. Consequently, the FCN/PI/VIS system achieved complete removal of acid orange 7 in 30 min, with a pseudo-first order reaction rate about 3.5 times higher than that of FCN/PI system. The involved reactive species were validated by scavenging tests, electron paramagnetic resonance (EPR) analysis, Raman spectra and electrochemical measurements. Moreover, the light switchable FCN-based PI activation system exhibited high recyclability and practicability for the treatment of various organic pollutants in water. This study provides new insights into the PI activation-mediated wastewater treatment processes.