In this present work, Polyaniline (PANI) and Polyaniline-Niobium Pentoxide (PANI-Nb2O5) composite were synthesized separately at room temperature by chemical polymerization of aniline without/with Nb2O5. Comparative study of XRD pattern of PANI and the composite confirms superficial deposition of PANI on Nb2O5 and the average size of the composite particle was found to be 10 nm. Aggregated granular morphology of the composite as compared to pristine PANI was confirmed by SEM images. Sensitivity of PANI-Nb2O5 composite to humidity at room temperature was tested using digital LCR meter at a selected frequency of 100 Hz and the results showed consistent variation in impedance from 60 KΩ to 360 KΩ within the relative humidity (RH) range 25% - 95%. Further, the response and recovery time of the composite were measured to be 80s and 90s respectively and the composite showed stable sensing ability over a period of one month.