In this study, eight different painted stainless steel 304L specimens were laser-cleaned using different process parameters, such as laser power, scan speed, and the number of repetitions. Laser-induced breakdown spectroscopy (LIBS) was adopted as the monitoring tool for laser cleaning. Identification of LIBS spectra with similar chemical compositions is challenging. A convolutional neural network (CNN)-based deep learning method was developed for accurate and rapid analysis of LIBS spectra. By applying the LIBS-coupled CNN method, the classification CNN model accuracy of laser-cleaned specimens was 94.55%. Moreover, the LIBS spectrum analysis time was 0.09 s. The results verified the possibility of using the LIBS-coupled CNN method as an in-line tool for the laser cleaning process.