A tellurium-based polymeric surfactant as a seleno-enzyme model has been constructed by employing 11-acryloyloxyundecyltriethylammonium bromide (AUTEAB, 4) and a tellurium-containing compound (1). It demonstrates strong substrate binding ability for thiols and high glutathione peroxidase (GPx) activity about 6 orders of magnitude more efficient than the well-known GPx mimic PhSeSePh in an ArSH assay system. More importantly, a series of tellurium-based polymeric micelle catalysts wit the catalytic tellurium center located at various positions in the micelle have been constructed, and the dramatic difference in activity indicates that the exact match of the catalytic center and binding site plays a key role in enzyme catalytic efficiency.