Nanostructured fiberglass based catalysts containing extra-low amount of Pt demonstrate high activity in the deep oxidation of propane. According to XPS and HAADF-STEM, highly dispersed 1–1.5 nm partially charged platinum species are confined in the bulk of fiberglass apparently as Pt2+–Pt0composites. Due to formation of Pt2+–Pt0species and involvement of molecular oxygen species in the reaction, which was proved by SSITKA studies with labeled oxygen, turnover frequency (TOF) of the deep oxidation of propane is 1–2 orders of magnitude higher than those for conventional supported Pt catalysts. It was also demonstrated that activity of fiberglass catalysts can be enhanced essentially when Pt is confined in the N-containing layer formed on the fiber surface via glass pretreatment with TMA hydroxide. The presence of TMA cations leads to the formation of more dispersed Pt species as compared to non-modified fiberglass and, as a consequence, to a twofold increase in the TOF of propane oxidation.