The C-C coupling reactions of aliphatic alcohols to aromatics and larger-mass compounds have large endothermicities and activation energies, calling for catalysts operating at high temperatures. Here, we demonstrate that plasmon-excited nanoparticles catalyze the C-C coupling of aliphatic alcohols at room temperature to produce polyaromatic hydrocarbons and graphene oxide. The conversion is quenched by radical and electron scavengers and by the surface passivation of metals, suggesting that the reaction proceeds through alkoxy, peroxyl, hydroxyalkyl, and alkyl radical intermediates created by the metal to molecule transfer of plasmonic hot carriers. Besides being the first realization of C-C coupling of aliphatic alcohols at room temperature, the result constitutes a rare example of an endothermic plasmon-induced reaction producing new bonds and a new method for photogenerating graphene derivatives. More importantly, the result demonstrates the facile generation of organic radicals directly from alcohols, which may be used as precursors for radical-based organic reactions.