Development of strategies for reproducible functionalization of inert graphene without adversely altering its structure and electronic properties is of key importance. Herein, we report a versatile approach for non-covalent functionalization of the basal plane of graphene, based on π–π interaction and click chemistry. The π system of alkyne-functionalized pyrene, as molecular “anchor”, adsorbs on graphene via π–π interaction; alkyne, as the terminal group, can be combined with azide on various substrate via click chemistry, copper (I)-catalyzed azide–alkyne cycloaddition reaction.