The rectifying behavior between graphene and semiconductors makes novel type of solar cells, photodetectors and light emitting diodes (LEDs). The interface between graphene and ZnO is the key for the performance of the optoelectronic devices. Herein, we find that green light emission is very strong for the forward biased graphene/ZnO nanowire van derWaals heterostructure.We correlated the green light emission with the surface defects locating at the ZnO nanowire surface through the detailed high resolution transmission electron microscopy and photoluminescence measurements. We pointed out engineering the surface of ZnO nanowires could bring a dimension of designing graphene/ZnO LEDs, which could be extended to other types of graphene/semiconductor heterostructure based optoelectronic devices.