Investigations of terpolymerization kinetics of the system on the basis of vinyl acetate (VA), peroxidic monomer (VEP) 2-tert-butyl-peroxy-2-methyl-5-hexene-3-yne, and acrylic acid proved that it falls under the equation of faintly inhibited copolymerization in which VEP serves as a comonomer and a chain-transfer agent. The contribution of each stage to the summary process rate is defined by the monomer ratio and depends on their consumption rate. Combination of a low-active VA monomer and of a VEP faint inhibitor in the system allows the control of the Trommsdorf effect and molecular-weight characteristics of functional oligoperoxides by changing the component ratio. The new carbon chain oligomers containing ditertiary alkyl peroxide and polar functional groups have practical application as multicenter surface-active radical initiators of polymerization and structurization.