2,2,6,6-Tetramethyl-4-piperidinyl methacrylate (TMPM), a new pentamethyl HALS 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (PMPM), their homopolymers (PTMPM and PPMPM), and their copolymers, [i.e., TMPM or PMPM copolymerized with monomers methyl methacrylate (MMA), methacrylic acid (MMA), acrylic acid (AA), and styrene (St) separately] were synthesized. PMPM shows an extremely excellent stabilizing effectiveness on improving the radiation resistance of polypropylene (PP) in comparison with other low molecular weight (LMW) HALS or polymeric HALS. Polymeric HALS shows a much higher thermal stability and better extraction resistance than that of LMW HALS. It is found that the Eb values of the PP-added pentamethyl HALS series are higher than those of PP with the corresponding tetramethyl HALS series at a given irradiation dose. A conclusion can be drawn that the pentamethyl HALS series has a higher stabilizing effectiveness than that of the tetramethyl HALS series.