Mean-square dipole moments, [mu2], of atactic poly(vinyl phenyl sulfide) (PVPS) [-CH2CHS-(C6H5)-]x were determined from dielectric permittivity measurements carried out in a fraction dissolved in benzene. The conformational analysis of the polymer suggests that both the stereoregularity and the rotational population about the backbone play a relatively minor role in the polarity of the chains. Contrary to what occurs with the unperturbed dimensions, the dipole moment of the polymer is conditioned by the conformational energy governing the incidence of the allowed orientations of the side groups.