A new species, Caloboletus xiangtoushanensis sp. nov., is reported from China. This medium-sized bolete is distinguished by a brownish orange to greyish yellow pileus, greyish yellow to olive yellow hymenophore that quickly stains blue when bruised, reticulate stipe, bitter taste and oblong to subfusoid basidiospores 9–13(–13.5) × 4–5 μm. On the basis of its morphological and molecular characters (ITS, nrLSU, tef1-α and rpb1), this novel taxon can be assigned to the genus Caloboletus, sister to Boletus taienus. Accordingly, a new combination C. taienus comb. nov. is also proposed in this study based on both morphological and phylogenetic evidence.