A new species Duvalius djokovici Ćurčić, Pavićević & Vesović is described, illustrated and compared with its closest relatives. It is tentatively placed in the subgenus Neoduvalius Müller, 1913. The new species is weakly pigmented, mid-sized, with no traces of eyes, with deep and complete frontal furrows, two pairs of elytral discal setae, and a distinctive form of aedeagus. It inhabits a subterranean site on Mt. Povlen (western Serbia), and is endemic to this mountain. We provide data on the distribution and biology of this new species. Additionally, we discuss the relations among other species of the subgenus Neoduvalius from western and southwestern Serbia, and provide a provisional key for their identification and an annotated list of Serbian Neoduvalius taxa.