In the study, CuO/ZnO/Al2O3 was prepared by sol-gel method. Its catalytic activity was evaluated by gas-phase catalytic dehydrogenation of 1,5-Pentanediol to δ-valerolactone as a probe reaction. CuO/ZnO/Al2O3 and long period reactive CuO/ZnO/Al2O3 were detected by XRD. Micro-structure and essence disciplinarian of CuO/ZnO/Al2O3 were disclosed. Metal ions had a cooperative effects during the catalytic dehydrogenation of 1,5-pentanediol to δ-valerolactone. After CuO/ZnO/Al2O3 deactivation, crystal particle size was increased clearly. It were found that characteristic diffraction peaks were caused by the catalyst temperature raising in methanol catalytic synthesis of ZnO. 1,5-Pentanediol and δ-valerolactone were detected by FTIR. Their internal chemical bond and molecular structure were disclosed. The purity of δ-valerolactone product was very high. δ-Valerolactone and its polymer were detected by DSC. δ-Valerolactone possessed with poor stability. Polymerization reaction was easily happened by itself. So it was worth focusing on how to improve the stability of the δ-valerolactone monomer. This study could provide basic data and experimental basis for gas-phase catalytic dehydrogenation of 1,5-Pentanediol to δ-valerolactone in pilot and industrial scale up research.