Covalent organic frameworks (COFs) are an emerging class of materials that have received remarkable attention as gas storage materials as a result of their continuous porosity, high surface area, and thermal resistivity. A review of the literature in the field reveals synthetic methodologies toward improving their gas storage capabilities by maximizing their surface area and pore size; yet their function as light-harvesting materials is relatively minimal. In pursuit of creating organic semiconductors capable of effective electron transfer pathways, COFs may be a possible alternative to achieve this goal with respect to their high degree of structural order. From these perspectives, the design of n-type perylene diimide (PDI) and ptype oligothiophene building blocks was developed. The synthesis of these compounds by transition-metal cross-coupling or lithiation-borylation protocols was explored, and these compounds show promising signs as potential candidates to form a new class of COF materials with photoconductive functions.