Photoinitiated metal-free controlled living radical polymerization of (meth)acrylates, and vinyl monomers was investigated using the polynuclear aromatic compounds pyrene and anthracene. Fluorescence spectral analyses along with nuclear magnetic resonance studies were performed to determine the rate constants of initiator radical formation and to investigate the mechanisms of polymerization. The obtained polymers were analyzed by spectral and chromatographic methods. Results show that the excited state anthracene undergoes a faster electron transfer reaction with the alkyl halide initiator than the excited state of pyrene. Pyrene excimers, which are formed at higher concentrations, also react with alkyl halides to form initiator radicals. Although pyrene monomers and excimers are acting slower, polymers with higher control over the chain end functionalities and molecular weight characteristics, are obtained in comparison to anthracene as sensitizer.