A novel tertiary amine catalyst (TAC) and trithiocarbonate (TTC) synergistic photo-induced controlled radical polymerization of methacrylates in the absence of conventional photoinitiators, metal-catalysts, or dye sensitizers, has been realized under mild UV irradiation (λ max ≈ 365 nm), yielding polymethacrylates with low molecular weight distributions and excellent end-group fidelity (> 95%).