This article reviews our work on the development and optimization of chiral, nonpolar media with large second-order nonlinear optical responses. We show how molecular engineering, theory, and measurements can be used to optimize this promising class of nonlinear optical materials. We describe how supramolecular alignment into easily processable materials takes advantage of the relevant molecular hyperpolarizabilities. A wide variety of techniques can be used to fabricate bulk materials belonging to the chiral nonpolar symmetry groups, D-infinity and D-2. The microscopic chromophore alignment schemes that optimize the nonlinear optical response in such materials are deduced from general symmetry considerations for both molecules and bulk. We also speculate on the possible applications of such materials as image-plane modulators. (C) 2003 Wiley Periodicals, Inc.