Nonlinear optics (NLO) is increasingly important for a variety of military and commercial needs ranging from new types of laser weapons to fiber optic communications networks, to optical computing applications. Rapid advances in optical phase conjugation, optical switching, and logic have demonstrated the enormous potential for practical applications with concurrent fast-paced materials development. The research has established that polyimides potentially have the excellent intrinsic properties and tailorability to meet the requirements of a wide range of nonlinear optical devices. The research described in this manuscript is a multidisciplinary effort to target key applications and material and processing requirements for these polymers. It discusses the synthesis, characterization, and processing of the nonlinear optical properties of polyimides which have been tailored for nonlinear optical activity.