This paper reports the synthesis of pyrene-azobenzene dyads using the Pd(II)-catalyzed directing group-assisted arylation of ortho C(sp2)-H bond of pyrene carboxamide as one of the key transformations. We have shown the synthesis of many examples of directly connected pyrene-azobenzene dyads (without any linker) and glycine-based azobenzene-pyrene dyads. At first, an acetanilide unit was incorporated in the pyrene skeleton through Pd(II)-catalyzed directing group-assisted ortho C(sp2)-H arylation by using iodoacetanilide. Then, the acetanilide moiety in the pyrene skeleton was transformed into an azobenzene unit to give the pyrene-azobenzene dyad. The UV-Vis spectroscopic studies have been performed to get the absorption properties (λmax (nm)) of all the compounds. Preliminary photoswitching studies in both forward and reverse directions and their related thermal reverse Z-E isomerization kinetics measurements were ascertained for representative compounds. Considering the importance of pyrene and azobenzene linked motifs as important chromophore-based photoswitchable molecules in chemical, materials, and supramolecular sciences research fields, this work enriches the library of pyrene-azobenzene dyads.