Nanostructured zinc sulfide ( ZnS ) thin films were synthesized in polyvinyl alcohol matrix by chemical bath deposition and self-assembly techniques. ZnS nanostructured thin films show second harmonic generation (SHG) under irradiation with a pico-second Nd :YAG laser system and the second harmonic intensity is higher for self-assembled nanotree like structured ZnS thin film in comparison with that from chemical bath deposited thin film. Under nanosecond laser pulses, thin films possess good saturable absorption behavior. The optical bandgap and visible luminescence also get enhanced.