Using the polyol method and a thermal post-treatment, nanoporous tin dioxide (SnO2) were prepared at different hydrolysis ratio (h = n (H2O)/n (Sn)). The influence of the hydrolysis ratio on the structural, textural, optical and electrical properties of SnO2 nanopowders was investigated by employing a set of various techniques including Fourier Transform Infra-Red spectroscopy (FTIR), X-ray diffraction (XRD), transmission electron microscopy (TEM), Energy Dispersive X-ray spectroscopy (EDX), Scanning Electron Microscopy (SEM), Nitrogen Sorption Porosimetry and Impedance Spectroscopy. FTIR and EDX studies revealed that SnO2 species were obtained. Nanocrystallites of cassiterite, i.e. rutile-like tetragonal SnO2 structure, were formed after annealing in air at 700 °C and the average crystallite size increased from 12.8 to 29.1 when the hydrolysis ratio rose from 17 to 24. Moreover, TEM, SEM, and N2 sorption porosimetry investigations indicated that the sample prepared for h = 17 was composed of an aggregated network of almost spherical nanoparticles, the morphology and sizes of which changed with the increase in the hydrolysis ratio to h = 24 and the mesoporosity of which was found to be linked to the interparticle space. Moreover, this increase in mean nanoparticle size was accompanied by a decrease in the band gap value from 3.4 eV (h = 17) to 3.16 eV (h = 24). Finally, bulk conductivity dependence with temperature was found to follow an Arrhenius law for samples annealed at 700 °C with an activation energy of 0.65 eV for h = 17, 0.69 eV for h = 20 and 0.71 eV for h = 24 that is typical of SnO2 nanopowders.