Using both INDO/2 and INDO/CI methods, we have calculated the structure and UV-visible spectra of C-60/aniline (AN), a model of the experimentally studied C-60/N,N-diethylaniline (DEA). The aniline fragment is bound directly to a carbon atom of C-60, and the charge transfer from aniline to C-60 takes place. The calculated UV-visible spectra show new charge-transfer bands at 635-819 nm, which are comparable with experiment. On the basis of correct electronic spectra, calculations of the nonlinear second-order optical susceptibility beta(ijk) and beta mu have been performed using the INDO/CI method combined with a sum-over-states expression. The calculated beta mu, value is 3.217 X 10(-29) esu (omega = 1.91 mu m), which is in excellent agreement with observation.