In this work, a study of trap and recombination center properties in polycrystalline Cu2ZnSnS4 thin films is carried out in order to understand the poor performance in Cu2ZnSnS4 thin film solar cells. Thermally stimulated current has been studied in Cu2ZnSnS4 deposited by pneumatic spray pyrolysis method using various heating rates, in order to gain information about trap centers and/or deep levels present within the band-gap of this material. A set of temperature-dependent current curves revealed three levels with activation energy of 126 ± 10, 476 ± 25, and 1100 ± 100 meV. The possible nature of the three levels found is presented, in which the first one is likely to be related to CuZn antisites, while second and third to Sn vacancies and SnCu antisites, respectively. The values of frequency factor, capture cross section, and trap concentration have been determined for each center.