Early Paleozoic Sn mineralization is rarely reported in South China. Here we carried out the detailed studies of deposit geology, cassiterite U-Pb dating, muscovite geochemistry and H-O isotopes on the Early Paleozoic Lijia Sn deposit in South China to constrain its genesis. The Lijia Sn deposit is hosted in the Yuechengling granitic batholith and characterized by greisen-type and quartz vein-type mineralization. Four stages of alteration and veining are recognized according to mineral assemblages and crosscutting relationships: pre-ore tourmalinization and silicification alteration of the Lijia granite (stage I), cassiterite-tourmaline-quartz vein and associated cassiterite greisen (stage II), and post-ore calcite-quartz-fluorite vein and calcite veinlet (stage III and IV, respectively). Two generations of the cassiterite in the cassiterite greisen, identified by cathodoluminescence imaging, yield the U-Pb concordant ages of 430.5 +/- 3.7 Ma and 428 +/- 2.2 Ma, respectively. The zircon U-Pb ages and geochemical features of the Lijia granite as well as the characteristics of alteration and mineralization indicate that the Lijia granite is Sn-bearing one and brings about the Sn mineralization. H-O isotopic compositions of the quartz from the Lijia granite reveal that the magmatic fluids have the delta O-18 values of 10.6-10.7% and the dD values of 57% to 62%. The ore-forming fluids (delta O-18 6.5-7.4%, dD 64% to 69%) responsible for cassiterite precipitation are derived from the mixing of magmatic fluids with minor meteoric water whereas more meteoric water is involved in the post-ore calcite-quartz-fluorite vein stage. Based on mineral assemblages, internal textures and chemical compositions, muscovite is divided into four generations from early to late: the Mus 1 and Mus 2 in the cassiterite greisen, the Mus 3 in the cassiterite-tourmaline-quartz vein and the Mus 4 in the phyllic alteration in the stage III. From the Mus 1 to the Mus 3, muscovite Rb, Cs, Zn, Li, V, Sc and Ga contents gradually decrease whereas boron shows an increasing trend, which might have been caused by the successive precipitation of hydrothermal minerals such as muscovite. Significantly higher Sr and Ba contents of the Mus 2 than the Mus 1 are likely related to the decomposition of the K-feldspar and plagioclase in the host granite. The combination of the precipitation of the early mineral phases, the decomposition of K-feldspar and the involvement of a large amount of meteoric water gives rise to the decrease of W, Sn, B, Rb, Cs and Sr contents and the increase of Ba, Ti, Mg, Li, Sc, V, Cr, Ga, Nb and Ta contents of the Mus 4 in the stage III. A key mechanism responsible for the formation of the Lijia Sn deposit is the interaction between the ore-forming fluids and the host granite. This study confirms the Early Paleozoic tin mineralization event in South China.