A combined gas-phase electron diffraction and quantum chemical (B3LYP/6-311+G**, B3LYP/cc-pvtz, MP2/cc-pvtz) study of molecular structure of 2-nitrobenzenesulfonamide (2-NBSA) was carried out. Quantum chemical calculations showed that 2-NBSA has four conformers, two of which are stabilized by intramolecular hydrogen bond. The latter (with the S–N bond in a close to orthogonal position around the phenyl ring and differing from each other by staggered or eclipsed positions of the N–H and S=O bonds in the SO2NH2 group) presented in a saturated vapor over 2-NBSA at T = 433 (3) K in commensurable amounts. Experimental internuclear distances (Ǻ) for the staggered conformer are (Å): r h1(C–H)av. = 1.071(9), r h1(C–C)av. = 1.390(4), r h1(C–S) = 1.789(8), r h1(S=O)av. = 1.427(6), r h1(S–N) = 1.644(6), r h1(N–O)av. = 1.221(4), r h1(C′–N) = 1.487(8), r h1(N–H)av. = 1.014. Calculations at B3LYP/cc-pvtz level were performed to determine the structure and the energies of the transition states between conformers. It was shown that the conformer structures of free molecule differ from those of a molecule stabilized by intermolecular hydrogen bonds in a crystal. Influence of a substituent X (X = –CH3, –NO2) on conformational features of the ortho-substituted benzenesulfonamide was established.