Template-directed synthesis is Nature's way of synthesizing organic building blocks via non-covalent forces. Inspired by such a mode of synthesis, we are involved in developing a method that utilizes templates to direct the reactivity of molecules within hydrogen-bonded assemblies in solids. In particular, we have shown that the cocrystallization of resorcinol with trans-1,2-bis(4-pyridyl)ethylene produces hydrogen-bonded assemblies that undergo photochemical [2+2] reaction to produce the corresponding cyclobutane product, namely rctt-1,2,3,4-tetrakis(4-pyridly)cyclobutane in quantitative yield and gram amounts. This approach has conventionally utilized reactants based on pyridine functionality as a molecular recognition site. Consequently, most molecules constructed by way of template-controlled solid-state synthesis are pyridine derivatives. To explore possible alternatives to pyridines, we have decided to investigate benzoxazole and benzothiazole moieties as hydrogen-bond acceptor groups. We expect that such groups will act as hydrogen-bond acceptors, similar to pyridines, and also will be more amenable to post-synthetic modifications and, thus, enhance the synthetic scope of this method. This presentation will focus on our most recent results in using benzoxazoles and benzothiazoles as functional groups alternative to pyridines in template-controlled solid-state synthesis.