Hydrogen production from steam reforming of liquefied petroleum gas (SR-LPG) process was studied over nickel, platinum, rhodium, and ruthenium-based catalysts supported on CeO2–SiO2 (CS). BET surface area, X-ray diffraction (XRD), temperature programmed reduction (TPR) and X-ray absorption near edge spectroscopy (XANES) techniques were used to characterize the samples. The catalytic activity and stability of the samples during SR-LPG were measured at 400 °C and 600 °C, respectively. XRD data were used to estimate the average crystallite size of ceria, which was small in all samples. For Pt and Rh containing samples, no diffraction peaks related to the metals were identified, which suggests high dispersion of these metals on the support. TPR and XANES experimental results showed that the addition of metals promoted the reduction of ceria. The order of catalyst activity for during SR-LPG at 400 °C was: Rh/CS » Pt/CS > Ru/CS » Ni/CS. Pt/CS and Rh/CS samples exhibited lower deactivation than nickel and ruthenium catalysts for SR-LPG at 600 °C during 24 h. Catalysts deactivation was mainly due to carbon deposition. In situ XRD data collected during SR-LPG at 600 °C revealed small increases in the mean particle sizes of Ni(0) and Ru (0), which could be pointed out as an additional cause for faster deactivation of the Ru/CS and Ni/CS catalysts.