An agro waste‐derived, ‘water extract of pomegranate ash’ (WEPA), has been utilized for the first time as a renewable medium for Pd(OAc)2‐catalysed Suzuki–Miyaura cross‐coupling at room temperature. This method offers a simple and sustainable synthesis of biaryls from aryl halides and arylboronic acids under ligand‐ and external base‐free aerobic and ambient conditions. This method has been found effective for both activated and unactivated aryl halides in the production of biaryls with moderate to nearly quantitative yields. The protocol shows high chemoselectivity over identical/similar reactive sites in aryl halides (i.e. selectivity over identical halogens or different halogens of aryl halides). This method exhibits high regioselectivity, i.e. the selective reactivity of a halogen over other identical halogens at different positions on the aromatic nucleus. Therefore, we disclose here a clean, benign, substantial chemo‐ and regioselective and highly economic alternative method for the palladium‐assisted synthesis of biaryls using an agro waste‐derived medium.