Photoconductive and third-order nonlinear optical properties exhibited by Cu2ZnSnS4 nanostructures are presented. The samples were synthetized in thin film form by a spray pyrolysis processing route. Distinctions in the photoconductive behavior throughout the samples were clearly noted by modulating their optoelectronic response dependent on electrical frequency. Vectorial two-wave mixing experiments were carried out at a 532 nm wavelength provided by a Nd:YAG laser system to study the optical nonlinearities in the samples. An induced transparency effect was observed during nanosecond single-beam experiments in the nanostructures reported. Quantum and thermal processes were considered to be the main physical mechanism responsible for the photo-electrical phenomena and nonlinear refraction in the nanostructures. Potential applications for developing nanophotonic and nanoelectronic instrumentation systems can be contemplated.