A finite field method to examine the polarizability and hyperpolarizabilities of individual molecular orbitals under the influence of an applied static electric field vector has been tested on two molecules, HF and C2H2 The results indicate that core sigma orbital’s can be significantly more (hyper)polarizable than valence and pi orbitals but may not contribute significantly to the total (hyper)polarizability. The effect of local environmental effects on valence orbitals can be qualitatively and quantitatively examined.