The optimized geometries, electron affinities, and dissociation energies of the alkylthio radicals have been determined with the higher level of the Gaussian-3(G3) theory. The geometries are fully optimized and discussed. The reliable adiabatic electron affinities with ZPVE correction have been predicted to be 1.860 eV for the methylthio radical, 1.960 eV for the ethylthio radical, 1.980 and 2.074 eV for the two isomers (n-C3H7S and i-C3H7S) of the propylthio radical, 1.991, 2.133 and 2.013 eV for the three isomers (n-C4H9S, t-C4H9S, and i-C4H9S) of the butylthio radical, and 1.999, 2.147, 2.164, and 2.059 eV for the four isomers (n-C5H11S, b-C5H11S, c-C5H11S, and d-C5H11S) of the pentylthio radical, respectively. These corrected EAad values for the alkylthio radicals are in good agreement with available experiments, and the average absolute error of the G3 method is 0.041 eV. The dissociation energies of S atom from neutral CnH2n+1S (n = 1-5) and S(-) from corresponding anions CnH2n+1S(-) species have also been estimated respectively to examine their relative stabilities.