Cu(In, Al)Se₂ thin films were prepared by electrodeposition from the aqueous solution consisting of CuCl₂, InCl₃, AlCl₃ and SeO₂ onto ITO coated glass substrates. The as-deposited films were annealed under vacuum for 30 min at temperature ranging between 200°C and 400°C. The structural, composition, morphology, optical band gap and electrical resistivity of elaborated thin films were studied, respectively using x-ray diffraction, energy dispersive analysis of x-ray, scanning electron microscopy, UV spectrophotometer and four-point probe method. The lattice constant and structural parameters viz. crystallite size, dislocation density and strain of the films were also calculated. After vacuum annealing, x-ray diffraction results revealed that all films were polycrystalline in nature and exhibit chalcopyrite structure with (112) as preferred orientation. The film annealed at 350°C showed the coexistence of CIASe and InSe phases. The average crystallite size increases linearly with annealing temperature, reaching a maximum value for 350°C. The films show a direct allowed band gap which increases from 1.59 to 1.78 eV with annealing temperature. We have also found that the electrical resistivity of films is controlled by the carrier concentration rather than by their mobility.