A self-regulated degradation system using polyion complexation through oxidation reaction from degradation products was preliminarily studied. 1,4-Dihydronicotinamide-modified dextran (NAH-Dex) with different molecular weights was prepared, and NAH moiety in NAH-Dex was oxidized by H2O2 to the dehydrated form (NA+-Dex). The dependence of stoichiometry, concentration, and molecular weight on polyion complexation with carboxymethyl dextran (CMD) were examined. NA+-Dex with a molecular weight above 40000 formed an insoluble complex with CMD, and the complexation was found to proceed stoichiometrically. The extent of polyion complexation was dependent on the concentration of NA+-Dex and CMD, whereas the time to reach complexation was dependent on H2O2 concentration. When H2O2 and dextranase were added to the solution containing NAH-Dex, CMD, and dextran, transmittance dropped and then increased again. From these results, the addition of dextran into the system of H2O2, NAH-Dex, CMD, and dextranase can regulate formation and dissociation of the polyion complex between NA+-Dex and CMD. The antagonistical inhibition of the degradation of the polyion complex is a key parameter of the self-regulated degradation system.