Cyclopentadienes (CPs) with Raman and electrochemically active tags were patterned covalently onto graphene surfaces using force-accelerated Diels-Alder (DA) reactions that were induced by an array of elastomeric tips mounted onto the piezoelectric actuators of an atomic force microscope. These force-accelerated cycloadditions are a feasible route to locally alter the chemical composition of graphene defects and edge sites under ambient atmosphere and temperature over large areas (similar to 1 cm(2)).