In the Triassic marine sediments, an obvious enrichment of lithium has been found. The source and enrichment mechanism of lithium is unknown. Here, we report trace and rare earth element and isotope analyses for Triassic sedimentary samples from core ZK601, recovered from the Huangjinkou anticline in the Xuanhan basin. Lithium concentrations from the Leikoupo and Jialingjiang formations are much higher than the average concentrations in the crust of eastern China and in other marine sediments. Lithium concentrations are highest at depths of 3300–3360 m (in argillaceous marine sediments), and Li is positively correlated with Rb, Ga, Zr, Nb and other trace elements. The range of δ7Li values in our samples is consistent with that in other Triassic marine carbonate rocks. Lithium concentrations and isotope ratios are negatively correlated in the argillaceous dolomite samples at depths of 3300–3360 m. We compared the results in this study with trace and rare earth elements in the clay from Sichuan and Chongqing, and propose that the clay in the argillaceous marine evaporites from Huangjinkou formed via the hydrolysis of volcanic ash during Early–Middle Triassic volcanic eruptions into brine basins, during which clay adsorbed Li from the brine and formed Li-rich argillaceous dolomites. The addition and hydrolysis of volcanic ash in the evaporative brine is also related to the formation of a new type of polyhalite.