Enhancing sensitivity and hysteresis in capacitance humidity sensors is vital for precise, reliable, and consistent humidity control. This study explores this concern by incorporating polyvinylpyrrolidone (PVP) and SiO2 nanoparticles into a polyvinyl alcohol (PVA)-based ionic liquid gel polymer electrolyte (ILGPE), studying two capacitor types: ILGPE and SiO2 composite ILGPE (CILGPE) capacitors. These novel electrolytes use ammonium acetate as a plasticiser, 1-butyl-3-methylimidazolium bromide as an ionic liquid, SiO2 nanoparticles as a composite, and PVA and PVP as host polymers. Capacitors were characterised and modelled using impedance spectroscopy (IS), providing an electrophysical insight into their working principle. Sensitivity and hysteresis were evaluated within a 20–90% relative humidity (RH) range at 25 °C. The SiO2 CILGPE capacitor with PVP presented superior sensitivity and hysteresis, revealing the beneficial combination of SiO2 nanoparticles and PVP. These benefits are due to the creation of pathways that facilitate water molecule diffusion and crystallinity reduction in PVA-ILGPE. In particular, at 10 kHz, it demonstrates a calibrated capacitance sensitivity of 2660 pF/%RH and a hysteresis of 3.28 %RH. This optimised capacitor outperforms some previous humidity capacitive sensors in sensitivity while exhibiting low hysteresis.