The marine shale of the Upper Ordovician Wufeng Formation–Lower Silurian Longmaxi Formation is the main source rock and the target of shale gas exploration in the southern Sichuan Basin. The maturity of organic matter (OM) is a vital indicator for source rock evaluation. Due to the lack of vitrinite, the organic matter maturity of the Wufeng–Longmaxi Formations in the southern Sichuan Basin is difficult to accurately evaluate. In total, 33 core samples of the Wufeng–Longmaxi Formations in the southern Sichuan Basin were selected to observe the optical characteristics of solid bitumen and graptolites and measure their random reflectance. Simultaneously, Raman spectroscopic parameters of kerogen were also used to quantitatively analyze the change in maturity. By using Raman spectroscopic parameters as mediators, conversion equations between graptolite random reflectance (GR_or) and equivalent vitrinite reflectance (EqVR_o) were established. Taking the calculation results of EqVR_o as constraints, the tectono-thermal evolution history of Wufeng–Longmaxi Shale in the southern Sichuan Basin is constructed through basin modelling. The results show that the maturity of Wufeng–Longmaxi Shale in the western Changning, Luzhou-western Chongqing, eastern Changning and Weiyuan areas decreases successively. The EqVR_o falls in the ranges of 3.61%~3.91%, 2.92%~3.57%, 3.08%~3.25%, 2.41%~3.12%, and the average EqVR_o is 3.73%, 3.30%, 3.18% and 2.80%, respectively. Thermal evolution in western Changning was controlled by the thermal effect of the Emeishan mantle plume and paleo-burial depth, while the thermal evolution of other areas was mainly controlled by paleo-burial depth. This study provides a reliable parameter for the evaluation of thermal maturity and makes a more accurate calibration of the maturity of the Wufeng–Longmaxi Formations in the southern Sichuan Basin; it also expounds the factors for the differences in thermal evolution in different parts of the area.