The scorpion fauna of Libya is varied and endemic, but little explored. Our work is a contribution to the study into the ecology and distribution patterns of scorpions from the Misurata region (North Libya). Investigations were carried out at 12 sites between June 2019 and December 2020 using ultraviolet light. We sampled 96 adult specimens belonging to nine species: Androctonus amoreuxi (relative abundance “RA” = 2.08%), Androctonus australis (RA = 31.25%), Androctonus bicolor (RA = 9.33%), Buthacus arenicola, Buthacus sp. 1 and Buthacus sp. 2 (RA = 3.13%), Buthiscus bicalcaratus (RA = 10.42%) Buthus adrianae (RA = 18.75%) and Buthus orientalis (RA = 19.79%). This region is characterized by great scorpion diversity and high community evenness. Among the specimens belonging to the above-mentioned nine species, we noted two species of Egyptian Buthus: B. adrianae and B. orientalis, representing a new record for Libya, and classified as a very accidental species (Occ = 50%). By frequency of occurrence, the other species were assigned to different categories ranging from very accidental to the common ones. The Canonical Correspondence Analysis (CCA) performed to detect gradients in species composition and species-environment relations confirmed the existence of a close relationship between some species and their biotopes, i.e., scorpions of the genus Buthacus were associated with sandy habitats, while A. amoreuxi and A. australis were associated with desert conditions (scarce vegetation, low precipitation and elevation). However, the ecological preferences of B. bicalcaratus remain uncertain.