DNA barcode data support species identification, aid in local fauna inventories, and inform the management of protected areas and monitoring of invasive species. As part of the InBuiLT project (“Invertebrate Fauna of Bulgaria and Adjacent Regions – DNA-based Barcoding of Under-represented in Reference Libraries Taxa”), materials from several underrepresented invertebrate groups from Bulgaria and neighboring countries were collected and provided for sequencing. Among the sampled taxa, several rare ant species from Bulgaria were also collected and barcoded. One of them is Oxyopomyrmex krueperi Forel, 1911. It is a rare, thermophilous ant species distributed in arid grasslands of the northeastern part of the Mediterranean Basin and the Near East. It is a reported species for Bulgarian myrmecofauna from a single locality near the town of Tzarevo. Here, we present the first DNA barcodes (COI-5P region) for the species, based on four worker ants hand-collected in different colonies along the southern Black Sea Coast of Bulgaria near the town of Primorsko. Images, metadata, and four DNA sequences (658 bp) were provided to the Barcode of Life Data System (BOLD). Bioinformatics analysis revealed three distantly related Oxyopomyrmex spp., with approximately 90% identity, confirming the genetic distinctiveness of the species. The phylogenetic relationships based on DNA barcodes with the currently available closest species are discussed. These findings represent the first global molecular record for O. krueperi and expand the known range of the genus. The data provide a valuable reference for future taxonomic and phylogenetic studies on Myrmicinae ants from arid and semi-arid regions.