The Baimashan granitic complex,located in the intersection of the NE-trending Xuefengshan arc uplift and the EW-trending Baimashan-Longshan-Ziyunshan structural belt, consists of Shuiche, Longtan, Xiaoshanjiang, and Longcangwan granite units. Zircon LA-ICP-MS U-Pb dating reveals that the Shuiche, Longtan, Xiaoshanjiang and Longcang units were emplaced at 424.9 +/- 2.2Ma, 228.2 +/- 1.3Ma, 225.3 +/- 1.1Ma and 215.0 +/- 1.2Ma, respectively. Granites from the Longtan and Xiaoshajiang units are metaluminous to weakly peraluminous with low Si and alkali contents. They are strongly enriched in Rb, Th, U and Pb, but depleted in Nb, Sr, P and Ti. They are characterized by relatively high REE concentrations with weakly Eu negative anomalies (delta Eu = 0.55 similar to 1.07). All samples from Longtang and Xiaoshajiang units exhibit high (Sr-87/Sr-86)(i) values (0.741441 similar to 0.748761), and negative epsilon(Nd)(t) (-10.5 similar to -9.4)and epsilon(Hf)(t) (-11.5 similar to -3.5) values with Proterozoic two-stage Nd (1.76 similar to 1.85Ga) and Hf (1.42 similar to 1.83Ga)model ages. In contrast,granite samples collected from the Longzangwan unit are strongly enriched in Rb, Th, U, Ta and Pb, but depleted in Ba, Nb, Sr, and Ti, with strongly Eu negative anomalies (delta Eu = 0.28 similar to 0.51). The samples usually have relatively high (Sr-87/Sr-86)(i) values (0.741441 similar to 0.748761), negative epsilon(Nd)(t) (-11.3 similar to -10.7), and epsilon(Hf)(t) (-11.5 similar to -3.5) values, with older Nd and Hf model ages of 1.87 similar to 1.91Ga and 1.47 similar to 1.97Ga, respectively. In combination with Sr-Nd-Hf isotopic and bulk-rock geochemical data,it can be concluded that the parental magmas of granites from the Longtan and Xiaoshajiang units were likely to be derived from the partial melting of the ancient intermediate-mafic meta-igneous rock and meta-sedimentary rock of the upper continental crust in South China. Granites of the Longcangwan unit were likely to be formed by reworking of meta-sedimentary materials and display S-type affinity. The Indosinian granites in the Baimashan granitic complex were probably emplaced under the extensional background after continental collision between the South China block and the Indo-China block. The Au-W deposits around the Baimashan complex are temporally and spatially related with the Indosinian granites, and therefore the Indosinian granites are potentially favourable for Au-W mineralization. The Indosinian granitic activities and related Au-W-(Sb) mineralization in central Hunan may be more prevalent and more intensive than conventionally considered during the past several decades.