Copper homoscorpionate complexes Tp(x)Cu(I)(NCMe) efficiently catalyze the Atom Transfer Radical Polymerization (ATRP) of methacrylatc (MMA) and other methacrylates at 50 degrees C in the absence of any reducing agents. Plots of M vs monomer conversion are linear with low molecular weight distributions (M-w/M-n = 1.09) being obtained. The effects induced by the TV ligand, the nature of the methacrylate substrate, the initiator and the temperature have been studied.