Co-based catalysts derived from the reduction of CoAl-layered double hydroxide (LDH)/g-C3N4 composite were investigated and used in the hydrogenation of γ-valerolactone to 1,4-pentanediol. The physicochemical properties of Co-based catalysts were analyzed and were compared with those derived from pristine CoAl-LDH and from CoAl-LDH/melamine and CoAl-LDH/activated carbon composites. Among the catalysts, the Co catalyst derived from CoAl-LDH/g-C3N4 had stronger and higher concentrations of Brønsted acid (H+), Lewis acid (Coδ+, δ>2), and Lewis base (N with a lone pair of electrons). The strong Lewis acidity and basicity were related to the enhanced turnover frequency. N-decoration was also found to improve the recyclability of Co-based catalysts.