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Polyaniline-CaTiO3 nanocomposites with their various weight percentages were prepared by chemical oxidative in situ polymerization technique. The prepared composites were characterized by Fourier transform infrared spectroscopy, scanning electronic microscope, and X-ray diffraction. The temperature-dependent dc conductivity of polyaniline-CaTiO3 nanocomposite was studied within the range of 40-200°C and found that 50 wt% shows high conductivity compared to other composites. Humidity sensor properties of polyaniline-CaTiO3 nanocomposite show better sensing properties and exhibit good linearity in sensing response curve, which discuss the implications of distortions and nonstoichiometry on their physical properties. Among all composites, 50 wt% of polyaniline-CaTiO3 nanocomposites show high sensitivity up to ~ 90% and their response-recovery times are 500 and 453 s, respectively.