In recent years, a series of rare metals and tungsten prospecting breakthroughs have been made in the northwestern Jiangxi. Especially, the Li- Rb enrichment and mineralization were reported for the first time in the Dahutang giant tungsten deposit. It shows an obvious distinction, probably a genetic relationship between the W and Li- Rb deposits. The Dahutang tungsten deposits have a characteristic of low grade, high tonnage, and strong hydrothermal alteration based on the identification of mineralogy of Li- mica and hydrothermal alteration type. The hydrothermal Li- mica are zinnwaldite (Li2O=4. 15%～4. 86%), protolithionite (Li2O=0. 81%～1. 72%), and Li- phengite (Li2O=0. 24%～0. 45%). We chose 47 altered hand specimens for whole rock geochemical analysis. Research shows that lithium mineralization is mostly responsible for the enrichment of Li- mica in the Dahutang tungsten deposit. The protolithionite and zinnwaldite altered Neoproterozoic granodiorite samples have a characteristic of high concentration of K2O (5. 94%～8. 06%), (Li2O=0. 34%～1. 548%) and Rb2O (0. 175%～0. 784%). However, the trilithionite, paragonite and albite Yanshanian altered porphyritic biotite granite have a characteristic of high concentration of Na2O (5. 79%～6. 17%)，Li2O (0. 902%～1. 034%), and Rb2O (0. 140%～0. 213%). Significantly, the unaltered Yanshanian granites have a characteristic of multi- phase magmatic activity, but all are enriched in Li, Rb, and W. Potentially, further enrichment and mineralization occurred due to hydrothermal fluid circulation. This work demonstrates a precipitation sequence from the magmatic Nb- Ta mineralization to Li- Rb, and finally to the W- Mo hydrothermal deposit. The preliminary study could provide a new direction for the regional and deep prospecting of rare metals in the tungsten deposit at the northwestern Jiangxi.