To reduce the externalities associated with the excessive use of carbon-fueled private vehicles, transport authorities and operators have recently been promoting one-way electric car-sharing services (ECS). Several studies attempted to identify the user acceptance and profiles of various car-sharing services, but there is a lack of consistent evidence of the psychological drivers of user acceptance. Based on an extension of the unified theory of acceptance and use of technology (UTAUT), this paper investigates the effects of six psychological constructs on behavioral intention to use ECS. Results from applying structural equation modeling to a survey with 656 respondents in the Netherlands show that social influence represents the most important driver of behavioral intention, followed by performance expectancy and personal attitude. It is also found that high satisfaction with the current means of transport for urban trips contributes to building trust in ECS companies, while car ownership has a negative indirect effect on behavioral intention. In response to the COVID-19 pandemic, the impact of hygienization measures on behavioral intention is considered. The result shows that respondents have a high degree of trust in ECS operators complying with cleaning requirements, which is translated into a lower degree of anxiety and consequently higher behavioral intention.