The synthesis of cyclopentanone from biomass furfural hydrogenation-rearrangement in water not only solves the problem of energy consumption, but also meets the requirements of green and sustainable development, thereby improving the utilization rate of biomass energy. This paper presented the synthesis of cyclopentanone from furfural hydrogenation-rearrangement using Co/Nb₂O₅ as the catalyst under the condition of water as the solvent. The suitable reaction conditions were determined through single-factor experiments as follows: catalyst amount of 0.15 g, mass ratio of furfural to water of 1:20, reaction temperature of 160°C, reaction pressure of 3 MPa, and reaction time of 5 h. Under these conditions, the furfural conversion was 100%, and the selectivity of cyclopentanone was 77.6%. To further optimize the reaction conditions and improve the yield of cyclopentanone, the response surface methodology was used to optimize the reaction conditions. The results showed that the relationship between the catalyst amount, reaction temperature, reaction pressure, and cyclopentanone yield could be expressed by a second-order polynomial. The correlation coefficient R^₂ of the model was 0.9845, indicating a good agreement between the predicted values and the experimental values. The optimized reaction conditions were: catalyst amount of 0.242 g, reaction temperature of 163°C, and reaction pressure of 2 MPa. Under these conditions, the furfural conversion was 100%, and the selectivity of cyclopentanone was 81%.