In this research, an integrated prediction-optimization approach (IPOA) was developed to manage coupled risks of water and energy nexus (WEN) systems. This approach combined Markov-chain based unbiased grey model (MC-UGM), Copula analysis and inexact optimization into a general modeling framework. The proposed approach was employed for dealing with the joint probability distributions of water and energy resources, and further supporting coordinated decision-making under uncertainties. Then, Beijing Tianjin Hebei Integrated Region (BTHIR), as the leading economic center of north China, was employed as the demonstrative site for the developed approach. Results indicated that IPOA could help predict water and energy demands, excavate the interactions between water and energy, identify and deal with the uncertain and complex features of the WEN system in the region. Optimal allocation schemes of water and energy under multiple coupled risks for multiple users in BTHIR were obtained. It can be found that under certain coupled risks, the lower for water risk, and the greater for energy risks. Also, the net benefits of WEN systems would continue to increase over time. Under most of the risk levels, water resource in BTHIR would be mainly allocated for domestic and industrial sectors. Energy resource would be mainly allocated for secondary and tertiary industrial sectors. The developed IPOA could not only realize the identification and quantification of inherent interactions between energy and water, but also help decision makers formulate reasonable policies balancing system benefits and coupled risks. Besides, IPOA can improve the robustness of utilization decisions regarding water and energy, which could help promote the coordinated development for BTHIR.