Autonomous vehicles (AVs) are entering the market, which will have a great impact on future decision making on mode choice in transportation systems. The aim of this study is to explore the determinants which influence travelers’ intentions to use AVs based on structural equation modelling (SEM). 310 valid sets of data from an online survey were collected to analyze factors which influence travelers’ intentions. Data analyses were conducted using IBM SPSS Statistics 23 and AMOS 23. The results showed that personality and preferences in relation to AVs are the main potential factors that cause travelers’ AVs use. Attitudes to modal services also affect intentions to use AVs. Personality has a significant positive effect on both attitude and preferences. The results provide exploratory empirical support for all hypotheses. The research results will help understand travelers’ choice motivation from psychological and service perspectives, and provide support for governments and enterprises to improve the management and services of autonomous vehicles.