A comprehensive analysis on the design, synthesis, and characterization of a novel ceramic nano-rod shaped ZnWO4–TiO2 porous composite electronic material has been manifested in this article. The cost-efficient high-temperature solid-state reaction route has been adopted for the synthesis mechanism. The composite’s unique structural and morphological features have been thoroughly investigated using X-ray diffraction (XRD) method, scanning electron microscope (SEM) imaging, and energy dispersive X-Ray (EDAX), revealing a distinct porous microstructure. The key electrical properties including dielectric constant, tangent loss, a.c. conductivity, impedance as well as electrical modulus have been analysed over a wide range of temperatures (35–400 °C) and frequencies (1 kHz–1 MHz). Moreover, the semiconducting properties and conduction process have been elucidated through the analysis of the ac conductivity spectrum, providing valuable insights into its electrical behaviour. The humidity sensing characteristics of the synthesized component have also been investigated at 25 °C at a frequency range of 100 Hz–1 MHz for a relative humidity range of 33–75%. The promising results highlight the immense potentiality of the ZnWO4–TiO2 porous composite as an advanced electronic material for humidity sensor applications in industrial, agricultural, and electronic fields.