A simple experimental method for determining optical second-order polarizabilities of organic molecules for second harmonic generation (SHG) is developed by using a two-level quantum mechanical model. Required values of excited-state dipole moments are obtained from a solvatochromic method based on the theoretical treatment of McRae. Second-order polarizabilities obtained by this method for a series of compounds compare well with those obtained by the conventional EFISH technique. The solvatochromic method has the important advantage that measurements can be made rapidly with simple equipment available in most chemistry laboratories. © 1989, American Chemical Society. All rights reserved.