We have focused on the conversion efficiency of CIGS thin film solar cell prepared by co-evaporation method as well as the optimization of process condition. The total thickness of back electrode was fixed at 1 ㎛ and the structural, electric and optical properties of CIGS thin film were investigated by varying the thickness of Mo:Na bottom layer from 0 to 500 nm. From the experimental results, the content of Na was appeared as 0.28 atomic percent when the thickness of Mo:Na layer was 300 nm with compactly densified plate-shape surface morphology. From the XRD measurements, (112)plane was the strongest preferential orientation together with secondary (220) and (204) planes affecting to the crystallization. The lowest roughness and resistivity were 2.67 nm and 3.9 Ω?㎝, respectively. In addition, very high carrier density and hole mobility were recorded. From the optimization of Mo:Na layer,we have achieved the conversion efficiency of 9.59 percent.