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Abstract CdSe semiconductor thin films were grown on indium tin oxide (ITO) coated glass substrates by co-electrochemical deposition method. Deposition potential was kept at − 0.95 V vs. Ag/AgCl reference electrode for ten minutes. Deposition electrolyte includes an aqueous solution of 10 mM CdCl 2 , 20 mM H 2 SeO 3 as precursors, 200 mM LiCl as complexing agent, and HCl for adjusting of pH. Deposited CdSe thin film was annealed at 500 °C for 30 min in air medium. Precursor and annealed CdSe thin films were characterized using a number of techniques, including SEM, EDX, XRD, UV–vis spectroscopy, and electrochemical impedance spectroscopy. SEM studies show that annealing alters the surface of precursor CdSe film from smooth to granular appearance. According to EDX analyses, the ratio of Cd/Se is close to 1.07 and 1.04 for the precursor and annealed CdSe thin film, respectively. XRD analysis shows that each film has polycrystalline structure. Precursor film has only cubic structure of CdSe, while annealed film has hexagonal structure of CdSe and cubic crystal phase of CdO. Optical energy band gap of the as-deposited CdSe film increases from 1.64 to 1.71 eV after annealing due to the mixture of the two phases. Refractive index against wavelength changes between 2.0 and 3.3. Calculations performed by using the data of Mott-Schottky measurements show that precursor CdSe film has 1.72 × 1016 cm−3, while annealed film is of 3.65 × 1017 cm−3 carrier concentration. The prepared films exhibit n-type semiconductor character. The study reports energy level diagrams of the produced semiconductor CdSe thin films by using the Mott-Schottky and Tauc's approximations. The carrier transport properties in the interface between active CdSe thin film and electrolyte are discussed based on an equivalent electronic circuit simulated to the Nyquist data of the CdSe/electrolyte system. [ABSTRACT FROM AUTHOR]