Electricity is one of the most widely used forms of energy. However, environmental pollution from electricity generation and the mismatch between electricity supply and demand have long been bothering economies across the world. Under this background, cross-border electricity trade provides a new direction for sustainable development. Based on the complex network approach, this paper aims to explore the structural characteristics and evolution of cross-border electricity trade networks and to figure out the factors influencing the formation of the network by using the more advanced network analysis method—ERGM. The results show that: (1) The scale of the electricity trade network is expanding, but there are still many economies not involved. (2) The centrality of the network shifts from west to east. The level of internal electricity interconnection is high in Europe, and Asian countries’ coordination role in cross-border electricity trade networks is enhanced. (3) Cross-border electricity trade helps to reduce CO₂ emissions, achieve renewable energy transformation, and reduce power supply and demand mismatch. Large gaps in GDP, electricity prices, industrial structure, geographical distance and institutional distance between economies are not conducive to form the cross-border trade network, while the common language is on the contrary.