e study of selective metal oxide-based binary/ternary systems has received increasing interest in recent years due to the possibility of producing e cient new ceramic materials for relative humidity (RH) detection, given the superior properties of the mixed compounds in comparison with pristine ones. e aim of this work was focused on preparation and characterization of non-doped and Nb 2 O 5 -doped TiO 2 : WO 3 pair (in the pellet form) and evaluation of corresponding humidity-dependent electrical properties. e microstructure of the samples was analyzed from scanning electron microscopy, X-ray di raction patterns, Raman spectra, BET surface area analysis, and porosimetry. e electrical characterization was obtained from impedance spectroscopy (100 Hz to 40 MHz) in the 10-100% RH range. e results showed that adequate doping levels of Nb 2 O 5 introduce important advantages due to the atomic substitution of Ti by Nb atoms in highly doped structures with di erent levels of porosity and grain sizes. ese aspects introduced a key role in the excursion (one order of magnitude) in the bulk resistance and grain boundary resistance, which characterizes these composite ceramics as a promising platform for RH identi cation.