A new type of humidity nanosensor based on LiCl-doped TiO2 nanofibers with poly(vinyl pyrrolidone) (PVP) nanofibers as sacrificial template has been fabricated through electrospinning and calcination. The sensor exhibited excellent sensing characteristics, such as ultrafast response and recovery times, good reproducibility, linearity, and environmental stability, which are of importance for applications in humidity monitoring and control.