An efficient route towards a heterogeneous transition metal-free catalytic C–H functionalization using a covalently linked graphene oxide–phenalenyl conjugate is described herein (28 examples, which include a core of some biologically relevant biaryl and hetero-biaryls). It is an environmentally benign, economical and heterogeneous platform, whose catalytic activity can easily be regenerated through a simple washing–drying technique and the catalytic activity can be retained even after 10 cycles.