Annealed film of ZnIn2Se4 has a homogenous nature with smaller roughness. ZnIn2Se4 film showed conduction mechanisms with ΔE1 = 0.44 eV and ΔE2 = 0.65 eV. Thermoelectric measurements showed a n-type polarity of ZnIn2Se4 thin films. J–V characteristics for Al/ZnIn2Se4/Al structure reveals three distinct regions. The trap-filled-limited voltage (VTFL) decreased with increasing temperature.