High-quality quantum-dot/polystyrene nanofibers (QD/PS NFs) are synthesized by drawing solvated PS doped with CdSe/ZnS QDs. As-drawn QD/PS NFs offer ultra-long-term photostability, flexibility, and excellent optical properties for sensing applications. Based on these active NFs, optical humidity sensors with extremely low power consumption, fast response, and long-term stability are successfully demonstrated, which may lead to a new category of nanometer-scale optical sensors.