CuGaSe2 thin films have been synthesized by one-step electrodeposition on titanium and SnO2/glass substrates from aqueous solutions that contain thiocyanate ion as a complexing agent. According to composition, and morphology analysis at deposition potential of -0.55V vs SCE (Standard Calomel Electrode) for 20 minutes from aqueous solutions of 4.6mM CuCl, 25.0mM GaCl3 y 9.2mM SeO2 in 2.0M de KSCN at pH 2.5 was found the optimum condition for obtain the CuGaSe2 thin films with good morphology and good stoichiometric. The samples were annealed at temperature of 520°C in inert atmosphere for 30 minutes to improve their crystallinity. The obtained CuGaSe2 thin film has a direct band gap (Eg) of 1.65eV. In addition, the cyclic voltammetry (CV) studies were performed in order to elucidate the electrodic processes that occur for the formation of semiconductor CuGaSe2. Therefore, the electrochemical behaviour for each ion (Cu+, Ga3+ and Se4+), for binary (Cu-Se, Ga-Se, and Cu- Ga) and for ternary (Cu-Ga-Se) systems are described. This material has potential application in solar cells.