We have fabricated degradable polyperoxides (PP) consisting of well-controlled 5,4-repeating units using various sorbic acid derivatives and molecular oxygen by an alternating radical copolymerization process. The PP obtained from the sorbic esters decompose via a radical chain reaction mechanism, leading to the formation of controlled low-molecular-weight products. In contrast, PP from some amide derivatives include an irregular chain structure, resulting in a more complicated degradation behavior. The theoretical calculations account for the selectivity in the two-step regiospecific propagation depending on the monomer structure. We have demonstrated the synthesis of functional PP based on two methods: one is the copolymerization of functional diene monomers with oxygen, and the other is the polymer reaction of PP including an azide group with a functional alcohol.