The use of organic polymers for nonlinear optical (NLO) processes is gaining increased attention because of the ability to engineer molecular structures that have high laser damage thresholds, high values of both the first and second hyperpolarizabilities, and inherently fast response times. This general class of materials also provides synthesis and processing options that are not feasible with inorganic crystals, such as structural optimization through modification, fiber spinning, film casting and thermoplastic processes. This paper provides the synthesis method for a class of polymers commonly referred to as the PBZ polymers. One of these polymers, namely polyp-phenylene-2,6-benzobisthiazole) (PBT) has been shown to have a high value of the macroscopic third order optical nonlinear susceptibility, X (3)1. Development of the synthesis of these π -electron conjugated systems combined with their evaluation for nonlinear optical responses may be viewed to be the preliminary step in the engineering of optimized materials for use in optical signal processing devices of the future. By describing the process of preparing rigid rod and semi-rigid benzothiazole and benzoxazole polymers in polyphosphoric acid (PPA) at the appropriate concentration to achieve the advantages of highly ordered solution morphologies, we establish the foundation for the preparation of materials with optimized figures of merit for NLO applications.