The emergence of electric vehicles (EV) presents new opportunities for transportation decarburization and sustainable transportation in cities worldwide. However, previous research has primarily focused on EV charging infrastructures within urban areas, with limited attention to those launched in expressway service areas. Addressing this gap is crucial in alleviating EV users’ range anxiety on expressway journeys. This study investigates the BEV users’ reuse behavior toward charging infrastructures on expressways. Focusing on the BEV users who had used the charging infrastructures on the expressway, the structural equation modeling and the multi-group analysis are employed to reveal the effect of psychological factors on BEV users’ reuse intention and explore the heterogeneity across different socio-demographic groups. Results reveal that Attitude and Subjective Norm drive the reuse intention. Perceived Risk has an indirect negative effect on reuse intention. Attitude has a more significant effect on reuse intention among elder users, high-frequency users, and low remaining State of Charge (SOC) users. This paper offers new insights for charging infrastructures’ planning and operation in expressway service areas.