In this paper, we report a synthetic protocol for the construction of biaryl motif-based or π-extended azobenzene and alkylated azobenzene derivatives via the Pd(II)-catalyzed bidentate directing group (DG)-aided C–H activation and functionalization strategy. In the past, the synthesis of biaryl motif-based azobenzenes was accomplished through the traditional cross-coupling reaction involving organometallic reagents and aryl halides or equivalent coupling partners. We have shown the direct coupling of C–H bonds of aromatic/aliphatic carboxamides (possessing a DG) with iodoazobenzenes as the coupling partners through the Pd(II)-catalyzed bidentate DG-aided, site-selective C–H functionalization method. Azobenzene-containing compounds are a versatile class of photo-responsive molecules that have found applications across branches of chemical, biological and materials sciences and are prevalent in medicinally relevant molecules. Accordingly, the synthesis of new and functionalized azobenzene-based scaffolds has been an attractive topic of research. Although the classical methods are efficient, they need pre-functionalized starting materials. This protocol involving the Pd(II)-catalyzed, directing group-aided site-selective C–H arylation of aromatic and aliphatic carboxamides using iodoazobenzene as the coupling partner affording azobenzene-based carboxamides is an additional route and also a contribution towards enriching the library of modified azobenzenes. We have also shown the photoswitching properties of representative compounds synthesized via the Pd(II)-catalyzed directing group-aided site-selective C–H functionalization method.