H-1 NMR spectra of poly(methyl methacrylate) prepared with benzoyl peroxide in toluene at 100 degrees C were measured on a 750 MHz high-resolution NMR spectrometer. End groups resulting from initiation, chain transfer, and termination reactions were assigned, and the numbers of end groups per polymer molecule were estimated. End-group signals showed splittings due to stereochemical sequences near the chain ends, the analysis of which indicated that the raceme dad at the chain end attached with C6H5- was higher than that with C6H5COO-.