We have synthesized and characterized structural, morphological, and transport properties of three members of bismuth ferrite family. We have observed a colossal changing in the electrical resistivity of Bi25FeO39 due to humidity adsorption/desorption on the surface of the sample. We suggest that this promising humidity sensing behavior effect is enhanced by the presence of a framework structure that contains electrically polarized Bi3+ cations along with short-range ordered oxygen-vacancies. As a consequence, Bi25FeO39 compound is a real candidate for humidity sensing properties.