The characteristics of laser-induced breakdown spectroscopy (LIBS) such as short measurement time and no sample preparation provide clear advantages over other analytical techniques for rapid elemental analysis at manufacturing sites where the composition of products need to be determined in real-time for process monitoring or quality control. Thin film solar cells based on CuIn1-xGaxSe2 (CIGS), polycrystalline compound semiconductor material, have unique advantages of high efficiency (>20%), long-term stability, and low manufacturing cost over other types of solar cell. The electrical and optical properties of the thin CIGS films are closely related to the concentration ratios among its major constituent elements Cu, In, Ga and Se such as Ga/(Ga + In) and Cu/(Ga + In), and thus an accurate measurement of the composition of CIGS thin films has been an issue among CIGS solar cell researchers, requiring a fast and reliable technique for composition analysis. This paper presents the results of nanosecond (ns) and femtosecond (fs) laser based LIBS analysis of thin CIGS films. The critical issues for LIBS analysis of CIGS thin films such are discussed in comparison with ns- and fs-LIBS measurement results. The calibration of LIBS signal intensity ratios with respect to reference concentration data is carried out and the results of optimal line selection for LIBS analysis, depth profiling capability, and reproducibility are discussed.