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The present paper proposes a reliable alternative for the increasing stability of polypropylene (PP) by modified polyhedral oligomeric silsesquioxanes (POSS). The chemiluminescence measurements and FTIR records point complementarily out the determinant influence of substituents on the progress of oxidation during the accelerated degradation caused by γ-irradiation. The main kinetic approach of oxidation acting in radiation-induced aging recommends some of the studied structures of modified POSS as appropriate compounds for improving stability of polypropylene at low additive concentration. The analysis of the present results is based on the implication of substituted POSS, whose contribution to the limitation of oxidation is conditioned by the influence of substituents. The delay of the oxidative degradation in studied γ-irradiated polypropylene is the consequence of the interaction between molecular PP fragments and the silanol moieties generated during radiolysis, which are the most vulnerable points of POSS structure.