Novel propeller-like multicomponent microstructures, which are actually self-assemblies of nanoparticles of poly(vinyl alcohol) (PVA)-coated Ag and/or Cu2O, were synthesized in aqueous solution of amphiphilic polyvinylacetone (PVKA) (ketalization degree D-H = 0.549), via one-step in situ reduction of Ag+ and Cu2+ under gamma-ray irradiation, utilizing the low hydrolysis rate of PVKA in the dilute acidic solution. Herein, PVA chains are obtained from hydrolyzed PVKA. The reaction mechanism and the formation mechanism are proposed. The room temperature photoluminescence spectrum has also been applied to explore the optical property.