Selenium (Se) has been called the “longevity element” by the scientific community because it has anti-cancer, anti-inflammatory, and anti-oxidant activity in humans. The geochemical properties and biological functions of Se have been widely studied in various fields, including geology, agriculture, and medicine. Bama Yao Autonomous County (Bama), a typical township in China with high longevity among the population, was selected as the research area. The present study organically combines the geological background, dietary structure, absorption and metabolism, and other biogeochemical aspects to comprehensively analyze the anti-aging properties of Se under high-Se conditions and a fiber-rich polysaccharide diet. Biogeochemical samples of surface soil, food, human hair, and urine were systematically collected from the environment and the residents, and the content and speciation of Se were analyzed. Concentrations of Se in the soil were moderate to high for Bama, with high-Se soil in 77.21% of the samples. Water-soluble Se concentrations were also high, 90% of the samples with moderate to high Se, and had a significant positive correlation with Se concentrations in crops. With both high total and high available Se, dietary samples from the study area showed Se-enriched characteristics. Accordingly, Se intake was also high (82.54 μg/d) in the population, strongly maintaining the normal bodily functions of the elderly. Accumulation and metabolism of Se in the population were assessed based on concentrations of Se in the hair and urine of residents over 60 years old. Continuous accumulation of Se was found to occur from 71 to 80 years of age. Concentrations of Se in residents under 71 years old and over 80 years old were in a state of loss. Overall, Se absorption and metabolism are maintained at the optimal physiological state, which is one of the primary factors maintaining the health and longevity of the elderly people in the study area.