In this paper, 61 sets of rice, peanut samples and their root soils were collected and systematically studied in the geological background of sandstone and mudstone in Yudu region of Jiangxi Province. The results showed that the average content of selenium in rice was 0.062 μg/g, the average content of selenium in rice roots was 0.39 μg/g, the average content of selenium in peanut was 0.051 μg/g, and the average content of selenium in peanut roots was 0.44 μg/g. In addition, the selenium enrichment rates of rice and peanut were 30.00% and 16.10%, respectively, corresponding to the root soil selenium content exceeding 0.4 μg/g accounted for 36.07%. Correlation analysis showed that there was a positive correlation between selenium content and TFe2O3, MnO, TOC, S, LOI, N, CaO, MgO, Na2O and negative correlation with SiO2. Crop selenium content was positively correlated with total selenium, bioavailable selenium, TOC, Fe-Mn oxides, calcium-magnesium compounds and sulfur contents, and use these properties to establish the geo-geochemical fitness model of selenium-enriched crops. Therefore, under the geological background that the soil parent material is sandstone and mudstone, the development of selenium-enriched agricultural products should not only be based on the total selenium content in the soil, but also consider the available selenium, TOC, Fe-Mn oxide, calcium and magnesium oxide, and sulfur content.