Anhydride-containing polyperoxides were synthesized by copolymerization of 5-tert-butylperoxy-5 -methyl-1-hexen-3-yne with either maleic anhydride or its blends with styrene. The integral composition of the polyperoxides was theoretically calculated as the copolymerization process proceeded and its direct experimental evidence was obtained. In macrochain-formation behavior, the process was found to be consistent with the generally accepted regularities of binary and ternary copolymerization. By employing their polymerizational transformations, water-soluble polyperoxides exhibiting surface activity and initiating properties were obtained. In aqueous solutions, such polyperoxide surfactants form micellelike colloidal structures. (C) 2000 John Wiley & Sons, Inc.