Three real-time composition monitoring methods in physical vapor deposition process of CIGS thin films were proposed. One is the detection of near infrared (NIR) transmittance through the CIGS films from the IR source such as a heater back side of the substrate. One is the detection of NIR reflectance of the incident light from the films. The other is the measurement of the substrate temperature during the preparation of the CIGS films. These methods utilize the difference of the carrier density between Cu-rich (∼ 1020/cm3) and (In+Ga)-rich ( > 1016/cm3) films. The NIR transmittance through and reflectance from the Cu-rich film decrease due to high free carrier absorption. The temperature of the Cu-rich films was lower than that of the (In+Ga)-rich ones under the constant heating power because the Cu-rich films have larger radiation in proportion to absorption. Therefore, the change of Cu/(In+Ga) ratios at stoichiometry can be monitored by the variation of the NIR transmittance, NIR reflectance or the film temperature in real time. These composition monitoring methods are very useful and easily applied to the physical vapor deposition process of the CIGS films for photovoltaic application. The solar cell with active area of about 0.5 cm2, fabricated by obtaining the CIGS film using the latter monitoring method, showed an efficiency of 17.0%.