In this paper, pulsed laser deposition (PLD) is attempted to be an alternative synthesis method for Cu-Ga-In (CIGS) thin films and the application of PLD on CIGS thin film solar cell materials was studied. Cu-In-Ga prefabricated metal films were grown on the quartz substrates by PLD method. Then the CIGS films with different Se content were synthesized by the post-selenization-annealing process. The structure, element component proportion and optical properties of the CIGS films with different deposition orders and thicknesses of the CuGa/In prefabricated metal layers were investigated. The experimental results indicate that, (1) The CIGS solar cell absorption layer with properties such as pure phase and high crystallinity can be obtained by PLD technique and Se-annealing processes. (2) The deposition order and thickness of prefabricated CuGa/In metal layers, as well as the Se-annealing temperature, have great influences on the crystallization, grain sizes and component proportion of the CIGS thin films. Compared to the CIGS film with In/CuGa double-prefabricated layers, the CIGS film with CuGa/In/CuGa trinal-prefabricated layers possesses better crystallization. (3) The prepared CIGS films all present low transmittance and high absorption coefficient in visible light region. Moreover, the largest value of Eg up to 1.21 eV was obtain in the CIGS films, which is higher than that in CuInSe ternary materials, and is benefit for the absorption of the high-energy photons in visible light. This work provided a novel technological method for obtaining the absorption layer of CIGS thin film solar cell with excellent performance.