A series of catalysts derived from silicotungstic acid (SiW) intercalated with CuZnFe hydrotalcite-like compounds (HTLCs) via ion-exchange method was prepared and characterized by N2-physisorption, XRD, TEM, SEM, H2TPR, FT-IR, and Py-IR spectra. The intercalation of SiW species into CuZnFe HTLCs was confirmed by these characterization techniques, while the catalytic performance was evaluated for glycerol hydrogenolysis. It was found that introduction of SiW significantly enhanced the selectivity towards 1,3-propanediols (1,3-PDO), owing to the increased Br?nsted acid introduction, as demonstrated by Py-IR analysis. The catalyst intercalating 30 wt. % SiW showed the highest selectivity (22.4%) to 1,3-PDO at 68.9% glycerol transformation. The catalytic performance was discussed and correlated with the physicochemical properties of these catalysts. The present contribution provides an economical approach to convert surplus glycerol from biodiesel manufacture to valuable propanediols.