China's Tianwen-1 Mars rover carries a laser-induced breakdown spectroscopy (LIBS) payload named MarSCoDe to analyze the mineral and rock composition on Mars. MarSCoDe is expected to experience a wide working temperature range of about 100 °C, which will lead to a spectral shift of up to ∼40 pixels (∼8.13 nm). Even worse, drastic changes in temperature and environment may cause a loss or increase of some spectral lines of an on-board calibration Ti target. An elastic particle swarm optimization (PSO) approach is proposed to fulfill the on-board spectral calibration of MarSCoDe under this harsh condition. Through establishing a standard wavelength set (SWS) and an individual particle wavelength set (PWS), and further elastically selecting a part of PWS to compare with SWS, the problem of spectral shift and number mismatch can be solved gradually with the evolution of the particle swarm. Some tests of standard lamps and Ti with MarSCoDe, placed in a Mars simulation environment chamber (MSEC) in a temperature range of 70 °C, were completed. Compared with the standard spectrum of the Ti target (obtained at 20 °C), the spectral shifts of the first, second, and third channels are approximately 0.33 nm (5 pixels), 0.85 nm (6.4 pixels), and 8.09 nm (39.8 pixels), respectively, at -40 °C before correction; after PSO correction, the spectral shifts are greatly reduced to up to 0.015 nm, and specially for the 626.28 nm line, the spectral shift is reduced from 8.09 nm to about 0 nm. Experimental results demonstrate that the PSO-based approach can not only correct the on-board spectral shift but also solve the number mismatch of spectral lines of MarSCoDe in the harsh working environment of Mars. Further, it can be extended to the on-board calibration of other spectral payloads for deep space exploration.