We investigated the multifaceted gas sensing properties of porous silicon thin films electrodeposited onto (100) oriented P-type silicon wafers substrates. Our investigation delves into morphological, optical properties, and sensing capabilities, aiming to optimize their use as efficient gas sensors. Morphological analysis revealed the development of unique surfaces with distinct characteristics compared to untreated sample, yielding substantially rougher yet flat surfaces, corroborated by Minkowski Functionals analysis. Fractal mathematics exploration emphasized that despite increased roughness, HF/ethanol-treated surfaces exhibit flatter attributes compared to untreated Si sample. Optical approaches established a correlation between increased porosity and elevated localized states and defects, influencing the Urbach energy value. This contributed to a reduction in steepness values, attributed to heightened dislocations and structural disturbances, while the transconductance parameter decreases. Simultaneously, porosity enhances the strength of electron‒phonon interaction. The porous silicon thin films were further tested as effective gas sensors for CO2 and O2 vapors at room temperature, displaying notable changes in electrical resistance with varying concentrations. These findings bring a comprehensive exploration of some important characteristics of porous silicon surfaces and established their potential for advanced industrial applications.