Organic-inorganic hybrid 3-(trimethoxysily) propylmethacrylate-co-platinum porphyrin-co-methacrylolsobutyl-polyhedral oligomeric silsesquioxane (TPMA-PtTPP-POSS) copolymer films were synthesized and applied as high-performance oxygen sensors. High sensitivity and fast response characteristics originate from the POSS-containing copolymer composition and wormlike structures. The wormlike structures composed of the POSS-containing copolymers selfassembled on the film surface can ensure the homogeneous dispersion of PtTPP and can be perturbed by a trace oxygen environment. Compared with the state-of-the-art PtTPP-TPMA film, the TPMA-PtTPP- POSS copolymer sensors exhibit a swift response (approx. 0.6 s), long-term stability, higher sensitivity (increased by 4-fold), and a relatively large dynamic range, etc. We believe that the POSS-containing hybrid films should provide a new strategy for designing sensitive and fast responding optical oxygen sensors.