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A fiber-optics tapered sensor that is covered by an electrospinning polyvinyl alcohol (PVA) nanofiber film, is demonstrated to measure humidity and temperature simultaneously. A section multi-mode fiber (MMF) was sandwiched between two leading-in and out single mode fibers (SMFs), which was further tapered down to 29 μm to promote the humidity sensitivity of the sensor. A thin layer of electrospinning PVA nanofiber film was uniformly coated on the MMF taper region by electrospinning technology. In order to promote the humidity sensitivity and mechanical strength of electrospinning nanofibers, the carbon nanotubes (CNTs) were mixed into PVA to formed PVA/CNTs composite nanofiber film. A Fiber Bragg Grating (FBG) was cascaded with the humidity sensing fiber to monitor the ambient temperature simultaneously. The addition of CNTs effectively eliminated the cracks on the electrospinning nanofiber and made it more uniform and smoother. As experimental results show, the humidity sensitivity of the sensor with PVA/CNTs film was 0.0484 dB/%RH, an improvement of 31.16% compared to that of the sensor with PVA film, for which sensitivity is 0.0369 dB/%RH. The nanofiber humidity-sensitive film constructed using electrospinning had a satisfactory humidity response, special 3D structure and extensive application prospect. [ABSTRACT FROM AUTHOR]