This study records and analyzes the diversity and structure of a snake assemblage in a transition area between Cerrado and Caatinga, in the municipality of Castelo do Piaui, state of Piaui, comparing the distribution and similarity of the species composition with other open localities already studied in Brazil. We used three complementary sampling methods: time constrained search (TCS), pitfall traps with drift fences (PFT), and incidental encounters (IE). During the TCS and PFT, 912 hours/observer and 6,468 days/trap were used, respectively. We estimated 23 species of snakes for the locality, although only 19 species were recorded. Philodryas nattereri Steindachner, 1870 (n = 10), Liophis poecilogyrus (Schlegel, 1837) (n = 9), Liophis viridis Gunther, 1862 (n = 8) and Thamnodynastes sp. (n = 8) were the most abundant species. Terrestrial, cryptozoic, and diurnal snakes predominated in the assemblage (Boidae = 2 species, Dipsadidae = 12, Colubridae = 2, Elapidae = 1, Viperidae = 2). The results indicate that the fauna of the locality is similar with that of other open formations, especially the Caatinga, corroborating previous floristic studies. Comparisons between snake assemblages analyzed by different authors suggest structural differences between the assemblages of the Cerrado and the Caatinga, contradicting the hypothesis of mixed composition of fauna in these biomes.