Twenty two N-(substituted phenyl)-methanesulphonamides of the general formula, CH 3 SO 2 NHR, where R = 4-XC 6 H 4 (X = H, CH 3 , F, Cl, Br or NO 2 ), i-XC 6 H 4 (X=CH 3 , Cl orNO 2 and i=2 or 3) and i, j-X 2 C 6 H 3 (i, j-X 2 = 2,3-(CH 3 ) 2 , 2,4-(CH 3 ) 2 , 2,5-(CH 3 ) 2 , 2,6-(CH 3 ) 2 , 3,5-(CH 3 ) 2 , 2,3-Cl 2 , 2,4- Cl 2 , 2,5-Cl 2 , 2,6-Cl 2 or 3,4-Cl 2 ) were prepared, characterized and their infrared spectra in the solid state and the NMR ( 1 H and 13 C) spectra in solution studied. The N-H stretching vibrations absorb in the range, 3298 - 3232 cm −1 . Asymmetric and symmetric SO 2 stretching vibrations appear as strong absorptions in the ranges, 1331 - 1317 cm −1 and 1157 - 1139 cm −1 , respectively. The sulphonamides exhibit S-N stretching vibrations in the range, 926 - 833 cm −1 . The effect of substitution in the phenyl ring in terms of electron withdrawing and electron donating groups is non-systematic. The 1 H and 13 C chemical shifts of N-(substituted phenyl)-methanesulphonamides are assigned to various protons and carbons of the compounds. Further, incremental shifts of the ring protons and carbons due to CH 3 SO 2 - and CH 3 SO 2 NH- groups in the N-(phenyl)-methanesulphonamide are computed and used to calculate the 1 H and 13 C chemical shifts of various protons and carbons of N-(substituted phenyl)-methanesulphonamides, by adding substituent contributions to the corresponding aromatic proton or carbon chemical shifts of either aniline, substituted anilines, benzene or substituted benzenes, in different ways, as per the principle of substituent addition. The computed values by different procedures agree well with each other and with the experimental chemical shifts. The correlation of these incremental shifts with the Hammett substituent parameters is poor.