In this paper, the detection accuracy of Laser-Induced Breakdown Spectroscopy (LIBS) technology under kHz laser conditions is verified, which is of great significance for the application of LIBS in the large-area, high-efficiency monitoring of laser paint removal processes. Firstly, a high-frequency (kHz) 1064 nm infrared pulsed fiber laser is used to clean the paint layer on aircraft skin. By integrating results from an energy spectrometer and atomic spectral database data, the impact of kHz lasers on the wavelength positions and the peak intensity of LIBS spectral lines is investigated, and the accuracy of LIBS technology is verified during kHz laser de-painting processes. The results indicate that the wavelength position of the kHz peak is shifted towards the blue-light region compared with that of the Hz peak, with a shift no greater than 0.18 nm. The spectral peaks between 380 nm to 425 nm disappear completely, and the signal-to-noise ratio of peaks within the 425 nm to 550 nm range decreases. The spectrometer test results corroborating with kHz LIBS spectra validate the detection accuracy under kHz laser conditions, demonstrating that LIBS technology can be used for monitoring the laser paint removal process on large aircraft skin areas efficiently. The study provides a reference for LIBS monitoring in kHz laser de-painting processes.