LiCl/SiO2-Al2O3 films with good humidity sensing properties were prepared by sol-gel process. The him structure was investigated by using XRD and AFM. The results indicated that the impedance variety of the him with nano-phase separation structure was more than 3 order of magnitude, and there was a better linear relationship between logarithmic impedance and relative humidity; the moisture absorption response and dehydration response of this film were less than 30s and 60s respectively.