Navigation systems are important in daily driving situations. The user experience of using navigation systems can influence drivers’ attitudes towards them and their intentions to use them. The objective of this paper was to identify the mechanisms underlying the use of navigation systems and analyse the psychological factors that influence drivers’ use of navigation systems. The technology acceptance model (TAM) was used to explore the factors impacting navigation system usage, and related factors such as trust and professional driver status were also considered. Using data collected from 372 drivers in China, the study demonstrated that two dimensions of the TAM, perceived usefulness (PU) and perceived ease of use (PEOU), as well as trust, were positively related to the intention to use navigation systems. Meanwhile, these positive associations were mediated by drivers’ attitudes towards navigation systems. Furthermore, professional drivers showed different trends from nonprofessional drivers in terms of the path from PEOU and trust to positive attitudes.