The genus Centroptilum Eaton, 1869 is widely distributed in the West Palaearctic region, but poorly diversified as it previously only encompassed two valid species, C. luteolum (Muller, 1776) and C. pirinense Ikonomov, 1962. The discovery of a new congener, C. volodymyri Martynov, Godunko and Palatov, sp. nov., is therefore remarkable; the new species is described based on larvae collected in Georgia, Turkey and Iran in 2012-2019. This new species can be distinguished by the structure of the cuticle with flattened, stretched shallow, triangular and semilunar-shaped corrugations; scales and their bases densely scattered on body surface; features of the mouth parts, including the presence of an expanded laterally labrum, in combination with segment III of maxillary palp and superlinguae of hypopharynx rounded apically, without any pointed projections at the tip; numerous small teeth scattered proximally in two rows along inner margin of the pretarsal claw; the shape of denticulation along the posterior margin of the abdominal terga, and the number of prominent posterolateral spines on tergum VII; and the shape of gills II-VII, with a distinctly concave posterior margin. Together with a morphological description, data on the distribution and mitochondrial cytochrome c oxidase subunit I gene (COI) barcode sequences of the species are provided. The species delimitation of C. volodymyri Martynov, Godunko and Palatov, sp. nov. and C. luteolum is tested using COI barcode sequences. The data obtained show that the new species can be distinctly recognised as a separate lineage. The habitat preferences associated with the different parts of the area of C. volodymyri Martynov, Godunko and Palatov, sp. nov. are described and compared. Distribution of C. volodymyri Martynov, Godunko and Palatov, sp. nov. confirms the connections between Caucasian and Asian fauna of Ephemeroptera, as already demonstrated in various families and genera. Short notes on the distribution of mayfly species common to the Caucasus, north-western Iran and Central Asia are presented.