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This work presents a new optical dual sensor based on PtTFPP-containing electrospun fibers and CsPbBr₃ perovskite quantum dots (PQDs) for simultaneous detection of oxygen (O₂) and nitric oxide (NO) gases, wherein PtTFPP-containing electrospun fibers for O₂ sensing was based on electrospinning process fabricated by platinum(II) meso-tetrakis (pentafluorophenyl) porphyrin (PtTFPP) complex immobilized in cellulose acetate (CA) matrix. CsPbBr₃ PQDs were used as NO-sensitive material and coated on the surface of PtTFPP-containing electrospun fibers. Both materials were excited by a UV LED with a central wavelength of 380 nm, and the fluorescence intensities of sensing materials were recorded and analyzed with a spectrometer. The experiment results show that the optical NO and O₂ sensors have linear Stern–Volmer plots, and the sensitivities are around 2.7 and 10.7, respectively. The response and recovery times of the optical NO sensor are 71 and 109 s, respectively. For optical O₂, response and recovery times are 60 and 65 s, respectively. The optical dual sensor with a new method based on fluorescent dye containing electrospun fibers and coated with CsPbBr₃ PQDs has been successfully developed to detect NO and O₂ gases simultaneously. The optical dual gas sensor provides great potential for practical applications with low cost and ease of fabrication.