In recent years, Chinese companies’ investment in overseas electric power has grown rapidly. Chinese enterprises with matured technology and abundant talent in the field of electric power and electric power investment are becoming the focus of Chinese enterprise investment. However, just like any other energy investment, electric power investment has various potential risks, including economic risk, financial risk, social risk, political risk, electric power foreground risk, resource risk, and environmental risk. To specifically measure electric power investment risk, this article proposed a nine-dimensional indicator system for countries along China’s ‘Belt and Road Initiative’. Moreover, a fuzzy integrated evaluation model ground on the entropy weight was established to evaluate the electric power investment risk of 21 countries along China’s Belt and Road Initiative. The result of research shows that electric power foreground and Chinese factors have become the major underlying determinants of electric power investment risk, while coal power economy, renewable power economy, and political risk should also be attached enough attention when making investing decisions. In conclusion, the optimal choices for China’s electricity investment are determined after balancing electric power foreground and basic factors. After analyzing investment risks of various countries, this paper puts forward policy suggestions, which can help Chinese enterprises avoid electric power investment risks and improve investment efficiency.