Marine shale in the lower Paleozoic is generally characterized by old age and high thermal evolution, which is the key stratum for exploration and development of shale gas in south China. At present, the reference materials(CRMs) of rock- eval and total organic carbon(TOC) analysis based on conventional conditions are difficult to meet the analysis of high thermal evolution samples, which severely restricts the progress of exploration and development of shale gas. For this study, mudstone and coal samples in the Longtan Formation are collected from Zhijin city in Guizhou. According to national primary reference materials specifications, two postmature sourcerock CRMs (GBW07499- GBW07500) have been developed, which give the certified values of S 2, T max and TOC. For the homogeneity test, the calculated F values in 2 rock- eval and total organic carbon CRMs obtained by analysis of variance (ANOVA) were less than the critical F values at the 95% confidence level, indicating no obvious differences between units and within units．The results showed that 2 CRMs had good homogeneity. The calculated test statistic b 1 of 2 CRMs during the 24- month observation period was statistically insignificant, indicating that 2 CRMs were stable. All the datas that 9 qualified laboratories were selected to give are in accordance with normal and approximate normal distribution and also equal accuracy. The standard materials provided certified values of S 2, T max and TOC with uncertainties: S 2=1. 09±0. 10mg/g, T max=633±3℃, TOC=26. 8%±1. 3%, S 2=6. 31±0. 48mg/g, T max=613±4℃, TOC=63. 1%±3. 4%. The CRMs can provide material basis for solving the problems of instrument calibration, method evaluation and data quality monitoring in the process of rock- eval and total organic carbon analysis, which effectively improve the quality of test datas.