AbstractStatic polarizability and second hyperpolarizability have been calculated for a number of small moleculesCO2, OCS, CS2, C2H2, C2H6, C3H8, cyclo‐C3H6, C3H4, C3H6, SiH4, Si2H6in the framework of the coupled‐perturbed Hartree‐Fock (CPHF) theory. The linear and nonlinear coefficients have been calculated with standard Gaussian basis sets and 3‐21G bases moderately enlarged with diffuse functions. It is shown that the parallel component of the polarizability saturates rapidly, which suggests that a 3‐21G basis containing s and p diffuse functions is sufficient to reproduce αzz. For the αxx and αyy components, a 3‐21G basis with s, p, and d diffuse functions is required. In general, the concordance between α computed with this basis set and the experimental static polarizability is at least of the order of 80%. On the contrary, the computation of the second hyperpolarizability with the same basis set for CO2, CS2, and C2H2 gives values that are 30% too low, compared to the experimental value. Better results are observed for ethane, propane, and cyclopropane for which the error is lower than 50%. The better agreement observed for the saturated compounds can probably be explained by their saturated character.