Flexible triboelectric nanogenerators (TENGs) are highly advantageous for human-centered monitoring due to their self-sustaining energy and high output performance. However, temperature fluctuations that limit thermal comfort have hindered their practical advancement. In this study, flexible titanium dioxide-silk fibroin@phase change microcapsule nanofiber films (TiO2-SF@PCM NFs) were successfully developed using an efficient electro-blown spinning (EBS) technique, with exceptional triboelectric output and superior temperature regulation capabilities. Our design achieved cooling effects of approximately 10 °C and provided thermal insulation of about 2.2 °C. Notably, applying the TiO2-SF@PCM NFs to a model car produced an impressive cooling effect of 22 °C. Furthermore, a single-electrode triboelectric sensor based on TiO2-SF@PCM NFs achieved a peak output power of ∼272 μW/m2 and exceptional stability over 1000 output cycles. This study presents a promising strategy for the scalable production of flexible composite nanofiber films, effective in both temperature regulation and self-powered monitoring, highlighting their potential for use as thermal comfort sensors.