Paleoenvironmental conditions significantly influence the distribution patterns and organic matter enrichment of shale. This study investigated the vertical variations of major elements, trace elements, and total organic carbon (TOC) in the Lower Carboniferous marine shale from the Yaziluo Rift Trough, South China, to understand the paleoenvironmental conditions, including redox conditions, terrigenous detrital input, paleoproductivity, and paleo-seawater depth. The Lower Carboniferous formation consists of three sedimentary facies: basin facies, lower slope facies, and upper slope facies. From the basin to the lower slope and then to the upper slope facies, TOC, quartz, and pyrite contents gradually decrease, whereas the carbonate mineral content shows an increasing trend. A continuous decline in paleo-seawater depth transformed a deep-water anoxic environment with high paleoproductivity and low detrital input in the basin facies into a semi-deep-water environment with dysoxic-oxic conditions and moderate detrital influx in the lower slope facies, evolving further into a suboxic environment with high detrital flux in the upper slope facies. The geochemistry results suggest that anoxic conditions and high paleoproductivity were the primary controls on organic matter enrichment in the siliceous shale of the basin facies. In contrast, redox conditions significantly influenced organic matter accumulation in the mixed shale of the lower slope facies, attributed to relatively low paleoproductivity in a more restricted marine setting. Additionally, the adsorption of carbon components by clay minerals facilitated the preservation of organic matter in the calcareous shale of the upper slope facies.