The increasingly massive consumption of plastics is becoming a global pollution disaster, with serious environmental and economic problems. Here we report an efficient and sustainable strategy for the visible-light driven upcycling of various plastic wastes into high-value-added formic acid. We firstly design and fabricate a self-assembly Z-scheme heterostructure of V-substituted phosphomolybdic acid clusters/g-C3N4 nanosheets (VPOM/CNNS). The Z-scheme charge transfer process is unambiguously elucidated by transient absorption spectra and electron spin resonance studies, which endow VPOM/CNNS heterostructure with efficient charge separation and strong redox potentials. Consequently, VPOM/CNNS heterostructure displays a superior photo catalytic performance toward upcycling of various plastics. The optimal VPOM/CNNS composite exhibits a remarkable formic acid production rate of 24.66 mu mol h(-1) g-1 for upcycling of polyethylene, which is 262-fold higher than that of pristine CNNS. This work highlights the potential of Z-scheme heterojunction as an unusual tool for the photo-driven upcycling of plastic waste.