Forty ring disubstituted phenylsulfamates have been synthesized as their sodium salts. These compounds display a variety of tastes including sweet, bitter and sour. Seven of them gave a predominantly sweet taste, twelve displayed a bitter taste followed by a sweet aftertaste, eleven showed predominant bitterness, five sourness and five gave an aniline- or hydrocarbon-like taste and were not assessed further by the panellists. A plot of z (width of molecule, measured using Corey-Pauling-Koltun (CPK) models) versus first-order molecular connectivity, 1chi(v) placed the seven predominantly sweet compounds on the line described by z = 2.27 1chi(v) - 0.158. Summation of Hammett sigma (sigma) values for the X and Y substituents gives SIGMA sigma, and with these the following structure-taste relationships were derived: Predominant sweetness: SIGMA sigma greater-than-or-equal-to 0.6, V(CPK) less-than-or-equal-to 300 angstrom3 and a meta-electron with drawing substituent, no para-substituent. Bitter/sweet aftertaste: SIGMA sigma less-than-or-equal-to 0.22, V(CPK) less-than-or-equal-to 300 angstrom3.Some of the starting disubstituted anilines have been reported to be sweet and sulfamation modifies or destroys this sweetness. This is also discussed.