The emission behavior of C-doped ZnO films, which were prepared by implantation of carbon into ZnO films, is investigated. Orange/red emission is observed for the films with the thickness of 60–100 nm. However, the film with thickness of 200 nm shows strong green emission. Further investigations by annealing bulk ZnO single crystals under different environments, i.e. Ar, Zn or C vapor, indicated that the complex defects based on Zn interstitials are responsible for the strong green emission. The existence of complex defects was confirmed by electron spin resonance (ESR) and low temperature photoluminescence (PL) measurement.