A new process through the coupling of maleic anhydride hydrogenation and cyclohexanol dehydrogenation has been studied for the simultaneous synthesis of c-butyrolactone and cyclohexanone. The possibility of the coupling process has been investigated thermodynamically. The separated hydrogenation of maleic anhydride, the dehydrogenation of cyclohexanol, and the coupling process over the same Cu-Zn-Al catalyst have been carried out in a fixed-bed reactor. Compared to conventional processes, the coupling process has several advantages, e.g., improved c-butyrolactone and cyclohexanone yields, good energy efficiency, and optimal hydrogen utilization. The effects of reaction temperature, n(H 2 )/n (reactants) and liquid hourly space velocity on the coupling process are investigated. One thousand hours of stability testing shows that the Cu-based catalyst has relatively high activity and good stability in the coupling process.