The preparation, X-ray crystal structures, and thermal analyses of five solvates of the non-nucleoside reverse transcriptase inhibitor Nevirapine are reported. Thermogravimetric traces for the solvates indicated the following compositions (N = nevirapine): N·(ethyl acetate)0.5 (1), N·(dichloromethane)0.5 (2), N·(toluene)0.5 (3), N·(water)0.5 (4), and N·(1,4-dioxane)1.5 (5). Centrosymmetric, hydrogen-bonded nevirapine dimers occur in the crystals of 1–3 and in a previously characterized, unsolvated form of the drug 6. In crystals of 4, drug molecules are linked by a single N–H···O═C hydrogen bond only, whereas solvate 5 contains noncentrosymmetric nevirapine dimers. Solvent molecules in 1–3 occupy channels, whereas the water molecules in 4 occupy isolated sites and 1,4-dioxane molecules in 5 occupy layers. These inclusion modes are described with reference to the thermal behaviors of the solvates recorded in TGA and DSC.