Valence topological charge-transfer (CT) indices are applied to the calculation of dipole moments. The algebraic and vector semisum CT indices are defined. The combination of CT indices allows the estimation of the dipole moments. The model is generalized for molecules with heteroatoms. The ability of the indices for the description of the molecular charge distribution is established by comparing them with the dipole moments of homologous series of percutaneous enhancers (phenyl alcohols and 4-alkylanilines). Linear and quadratic correlation models are obtained. CT indices improve the multivariable quadratic regression equations for the dipole moment. The variance decreases 97% (4-alkylanilines). No superposition of the corresponding G(k)-J(k)and G(k)(V)-J(k)(V) pairs is observed in the fits, which diminishes the risk of co-linearity. The inclusion of the heteroatom in the pi-electron system is beneficial for the description of the dipole moment, owing to either the role of the additional p orbitals provided by the heteroatom or the role of steric factors in the pi-electron conjugation. Inclusion of a conjugated double bond in the alkyl chain lends to more rigid structures with dipole moment variations lower than 1%.