As one of the most critical parameters to evaluate the quality and performance of mobile phones, real-time temperature monitoring of mobile phones’ integrated chips is vital in the electronics industry. Although several different strategies for the measurement of chips’ surface temperature have been proposed in recent years, distributed temperature monitoring with high spatial resolution is still a hot issue with an urgent need to be solved. In this work, a fluorescent film material with photothermal properties containing thermosensitive upconversion nanoparticles (UCNPs) and polydimethylsiloxane (PDMS) is fabricated for the monitoring of the chips’ surface temperature. The presented fluorescent films have thicknesses ranging from 23 to 90 μm and are both flexible and elastic. Using the fluorescence intensity ratio (FIR) technique, the temperature-sensing properties of these fluorescent films are investigated. The maximum sensitivity of the fluorescent film was measured to be 1.43% K−1at 299 K. By testing the temperature at different positions of the optical film, distributed temperature monitoring with a high spatial resolution down to 10 μm on the chip surface was successfully achieved. It is worth mentioning that the film maintained stable performance even under pull stretching up to 100%. The correctness of the method is verified by taking infrared images of the chip surface with an infrared camera. These results demonstrate that the as-prepared optical film is a promising anti-deformation material for monitoring temperature with high spatial resolution on-chip surfaces.