Polymeric microfibers, particularly the fluorinated copolymers’ fibers, are promising functional materials for photoelectric devices, sensing, and energy storage due to their various surface characteristics. However, to obtain the high fluorine content copolymer-based fibers with considerable uniformity is likely to be especially challenging, which seriously debilitates their applications in sensor devices. Herein, for the first time, we presented a high fluorine content platinum porphyrin-grafted poly(isobutyl methacrylate-co-dodecafluoroheptyl methacrylate) copolymers (PtTFPP-p(IBM-co-DFHMA)) microfibrous thin-films used as optical oxygen sensors. The porous thin-film frameworks were formed of uniform microfibers, which afforded an exceptional improvement in sensitivity and exhibited 584% higher sensitivity than the solid sensing film owing to the large specific surface area, porous structures and oxygen diffusion enhancement by fluorine elements. Additionally, the remarkable emission intensity-changing characteristic of the microfiber sensing film under various air pressures facilitates convenient visualization of pressure distributions on film surface. The characteristics are particularly important for the computational fluid dynamics simulations in various sensing fields such as unsteady flow visualization and unsteady pressure measurements, etc. Owing to its attractive advantages and versatile performance, fluorine-containing copolymers fibers are expected to provide a new strategy for the rational design of high performance gas sensor devices.