Based on the results of multipurpose regional geochemical surveys of the Guizhou Province, geochemical characteristics of soil Se and Se-rich land resources in the central area of Guiyang City were studied and evaluated. Major conclusions are as follows: (1) the Se content in surface soil of the central area of Guiyang City was 0.17–2.89 mg kg−1, and the average was 0.78 mg kg−1, which were respectively 2.6 and 3.9 times of the national background value of soil and the world background value of soil. The Se content in deep soil was 0.11–1.48 mg kg−1, and the average was 0.44 mg kg−1, which were respectively 1.5 and 2.2 times of the national background value of soil and the world background value of soil. The soil Se content decreased with the increase in the soil depth on the vertical profile, and the surface soil had a higher Se content. (2) Distribution of Se content was mainly affected by parent material, physicochemical properties of soil and other components, soil type, and land use type. Parent material played a key role, as the soil Se content was mainly originated from parent rock and increased with the background value of Se in parent rock, physicochemical properties of soil and other components had certain influences upon the Se content. Se was shown to have a significant linear positive correlation with S and organic carbon but no significant correlation with pH value. Se content varied with different types of soil as follows: skeleton soil > yellow soil > paddy soil > limestone soil > purple soil. Land use type also had certain influences upon the soil Se content as follows: dry land > construction land > garden plot > grassland = garden plot > forest land. (3) Taking 0.4 mg kg−1 ≤ ω (Se) <3.0 mg kg−1 as the standard for Se-rich soil, Se-rich soil of the study area covered an area of 2224 km2 and 92.5% of the total area; the remaining is general soil. The study area had no Se-excess soil. Therefore, the central area of Guiyang City has a high proportion of Se-rich land, a large area of Se-rich land resources, and a moderate selenium enrichment strength, which have been rarely seen anywhere and provide advantageous resources for the development of Se-rich featured agriculture.