Abstract: Energy and electricity are water-intensive industries, and the virtual water embodied in electricity is redistributed through interprovincial electricity exchange. This paper simulated the infinitely high-order interconnected grid network and the power sector’s virtual water transfer network by the complex network-based electricity exchange model. The results showed that the virtual water transfer network in the power sector was more tightly connected and complex than the direct power exchange network, with an increase in flow links by more than five times, which meant the existence of a large amount of indirect power exchange. In 2020, the virtual water embodied in interprovincial electricity transmission accounted for about 3% of the national water consumption in China. For large power-exporting provinces, supporting power supply outside the province increased local power sector water withdrawals by 20%~30%. Virtual water transfers embodied in interprovincial electricity transmission resulted in great changes in water pressure in six provinces including Beijing, Shanghai, Zhejiang, Anhui, Fujian and Hubei. In conclusion, the synergistic management between power resources and water resources is the top priority to ensure energy security and enhance climate resilience of the power system. A new pattern of synergistic development of power and water resources should be accelerated in the future.