Hybrid optical fibers have been widely investigated in different architectures to build integrated fiber photonic devices and achieve various applications. Here we proposed and fabricated hybrid microfiber waveguides with self-growing polymer nanofilms on the surfaces of microfibers triggered by evanescent field of light for the first time. We have demonstrated the polymer nanofilm of ∼50 nm can be grown on the microfiber with length up to 15 mm. In addition, the roughness of nanofilm can be optimized by controlling the triggering laser power and exposure duration, and the total transmission loss of the fabricated hybrid microfiber is less than 2 dB within a wide wavelength range. The hybrid polymer nanofilm microfiber waveguides have been characterized and their relative humidity (RH) responses have also been tested, indicating a potential for RH sensing. Our fabrication method may also be extended to construct the hybrid microfibers with different functional photopolymer materials.