As a semiconductor material, Cu(In,Ga)Se₂ (CIGS) nano film plays an important role in the field of solar cells. In this paper, a series of CIGS thin film samples were deposited using the magnetron sputtering technology under different sputtering powers, working pressures, and sputtering time. Laser-induced breakdown spectroscopy (LIBS) was quantitatively analyze the atomic concentration ratios of Ga to In+Ga and Cu to In+Ga in CIGS thin film samples. Then combined with the single calibration curve drawn under each sputtering parameter, a merged calibration curve of two content ratios was drawn, and the fitting coefficient of the merged calibration curve reached more than 0.99, indicating that the fitting effect is good. Moreover, the three samples of CIGS thin films under random sputtering parameters were used to assess the accuracy of LIBS by comparing the analysis results of energy dispersive X-ray spectroscopy (EDS) and LIBS. The errors of the analytical results were all less than 5%, verifying the accuracy of LIBS. This research provides a new method for the rapid analysis of CIGS thin film and the timely determination of performance and develops new applications of LIBS technology in the field of thin film semiconductor materials.