The Cretaceous-Palaeogene intertrappean deposits of the Deccan Volcanic Province of India comprise vertebrate, invertebrate and plant fossils of the dominantly continental realm. A 3–4 m thick shaly-sandstone lacustrine intertrappean sequence of Early Palaeogene (Palaeocene-Early Eocene) Bamanbor Formation, Chotila Basin (Saurashtra province, Gujarat State, western India) has yielded a collection of molluscans (bivalve and few gastropods) fauna. High-resolution digital photography and radiography of the recovered bivalves allowed us to gain detailed inferences on shell morphology. In a taxonomical context, we herein propose a new unionid molluscan superfamily Deccanoidea nov. represented by a single new family Deccanoidae nov. that includes two new subfamilies, that is, Deccanoinae nov. (represented by two new genera Deccanoida gen. nov. [including four new species: D. conrugis sp. nov., D. aleta sp. nov., and D. costaria sp. nov.] and Bamanboria gen. nov. [including one new species Bamanboria oblongis gen. et sp. nov.] and Chotiloinae nov. [represented by one new genus Chotilia gen. nov. and three new species: Chotilia trappeansis sp. nov., C. tuberculata sp. nov. and C. deccanensis sp. nov.]). Inorganic geochemistry of host (unionid-yielding) lithologies reveals oxic-freshwater conditions, humid-climate and moderate rainfall. The data on historical biogeography reveals that the Indian subcontinent hosted unionids during the late Cretaceous; however, the presence of new (at family/generic level) unionid fauna during the Early Palaeogene (Palaeocene-Early Eocene) in India indicates changes in the geographic position and ecologic condition linked to northward drift and lava outpouring, respectively. A disjunct distribution of unionid fauna in the erstwhile Gondwanan continents and insular India during the Cretaceous-Palaeogene interval can be explained in terms of both vicariance and dispersal.