Utilizing a hybrid waveguide comprising microfiber and graphene oxide (GO), this study introduced an innovative temperature sensor based on four-wave mixing (FWM) effect. The methodology involved a tunable continuous wave (TCW) laser and a self-engineered all-fiber mode-locked laser operating at 1560 nm. The microfiber, featuring a minimum diameter of 10 μm, was fabricated through the flame fusion tapering technique, and the microfiber surface was coated with a GO film through the spontaneous evaporation of a GO solution. To improve the stability and robustness of the sensor, a layer of polydimethylsiloxane (PDMS) was applied to the surface as a protective coating. The GO film compensated for dispersion in conjunction with microfiber, enhanced nonlinearity and facilitated low-power FWM phenomena. Furthermore, it increased temperature sensing sensitivity. By measuring the center wavelength shift of the idler and signal light, we achieved a temperature sensing sensitivity of −2.08 nm/℃ from −15 ℃ to 20 ℃ using the CW laser at 1540 nm. This sensor also had a resolution of 0.024 ℃, a response time of 0.12 s and a maximum temporal resolution of 0.08 s. Our study marks the initial investigation of a temperature sensing mechanism employing the FWM phenomenon within this unique hybrid waveguide. It serves as a proof of concept for using a microfiber combined with the two-dimensional material GO film to generate nonlinear FWM for temperature sensing. Continuous optimization of experimental conditions and waveguide dimensions is expected to enhance sensing performance. This opens up new avenues for future research in novel optical sensing technology, particularly in the exploration of high-performance sensors through the integration of nonlinear phenomena with different two-dimensional materials, showcasing substantial research potential.