Monitoring air quality is crucial for understanding and improving public health. There is interest in developing ultra-sensitive, low-power, cost-effective sensors. This work demonstrates that structural modulation of Sn nanoparticles through controlled deposition and oxidation enables a transition from metallic to semiconducting percolative networks, significantly enhancing NO₂ sensing performance at room temperature. The proposed percolation-driven sensing mechanism provides a new framework for understanding charge transport and gas interaction in nanostructured metal oxide systems. The nanoparticles are deposited near the percolation threshold for electrical conduction and, upon exposure to air, consist of a tin core and an amorphous Sn₃O₄ surface. Post-deposition heating in air at 320 °C for two hours forms SnO and Sn₃O₄ on top of the gold electrodes and polycrystalline SnO in the tetragonal litharge phase, known as Romarchite, on the glass between the electrodes. Both as-deposited and heat-treated sensors were capable of detecting NO₂ at room temperature, with a limit of detection in the parts-per-billion range. A percolation model is used to explain their operating currents, in which NO₂ reacts at nanoparticle gaps and intra-grain boundaries to form charge-depletion regions that primarily determine their resistance. Heat treatment has also been found to cause disproportionation of SnO, resulting in tin-rich precipitates and increasing the operating current to the milliampere range. These precipitates, although oxidized on their surfaces when exposed to air, may serve as bridges that reduce the total resistance of the percolating paths.