The stereochemistry of the chain end of poly(methyl methacrylate) prepared under group-transfer polymerization conditions and terminated with (CH3I)-C-13 in the presence of tris(dimethylamino)sulfonium difluorotrimethylsiliconate (TASSiMe3F2) is determined by C-13 NMR and compared with the tacticity of the chain. The propagation statistics reveal consistency with a Bernoullian process for the entire temperature range studied (-96 to +45-degrees-C), confirming previous reports based on main-chain triad tacticity alone. The results suggest that the E and Z stereoisomers demonstrated for these systems propagate with identical stereochemistry and show that a comparison of the stereochemistry of the end group and the main chain is a valuable method for analyzing the stereochemical statistics of vinyl polymerization.