Herein, we report the design, synthesis, and characterization of two novel N-annulated perylene diimide (NPDI) tetramer arrays that were developed using copper catalyzed alkyne-azide cycloaddition. Despite the optoelectronic properties of both tetramers being nearly identical, the two tetramers exhibited very different molecular geometries. The twisted spirobifluorene NPDI tetramer (sbfNPDI 4 ) was found to have an extended and flexible geometry, while the planar pyrene NPDI tetramer (pyrNPDI 4 ) exhibited a highly congested and conformationally locked geometry. Organic photovoltaic devices were constructed to demonstrate the use of both new compounds as electron acceptor materials, where slightly higher power conversion efficiencies were achieved with pyrNPDI 4 than sbfNPDI 4 . This study highlights the viability of using "click" chemistry as a facile synthetic strategy towards the development of new multicomponent perylene diimide materials for organic electronic applications.