In this study, the sensing properties of palladium-doped porous silicon (Pd/p-Si) substrates for low-ppm level detection of toxic H 2 S gas are investigated. A Si substrate with dead-end pores ranging from nanoto macroscale was generated by a combined process of metal-assisted chemical etching (MacE) and electrochemical etching with tuned reaction time, in which nano-Pd catalysts were decorated by Ebeam sputtering deposition. The sensing properties of the Pd/p-Si were enhanced as the thickness of the substrate layer increased; along with the resulting variation in surface area, this resulted in superior H 2 S sensing performances in the low-ppm range (less than 3 ppm), with a detection limit of 300 ppb (sensitivity 30%) at room temperature. Furthermore, the sensor displayed excellent selectivity toward the hazardous H 2 S molecules in comparison with various other reducing gases, including NO 2 , CO 2 , NH 3 , and H 2 , showing its potential for application in workplaces or environments affected by other toxic gases. The enhancement in sensing performance was possibly due to the increased dispersion and surface area of Pd nano-catalysts, which led to an increase in chemisorption sites of adsorbate molecules.