The number of tunnel fire accidents has increased with the scale of expressway tunnel construction and traffic flow. Due to the severity of tunnel fires, improving tunnel fire safety and reducing fire accident hazards has become a societal concern. It is essential to explore and evaluate tunnel fire safety literacy among the population. In this study, an online and on-site questionnaire survey was conducted in Hunan Province, China. A total of 1990 questionnaires were collected, of which 1573 were valid. Overall statistical analysis, descriptive statistics, and correlation analysis were performed on valid questionnaires. The results show that the overall level score rate of awareness of drivers and passengers regarding tunnel fire safety was only 0.43. In total, 58.42% of people were unaware of the pedestrian cross passages in expressway tunnels, and 68.40% were unable to recognize them. Similarly, 46.47% of people were unable to recognize evacuation signs in expressway tunnels. In addition, 39.29% of people chose the wrong evacuation behavior. The percentage of people who were aware of the correct usage of firefighting facilities in expressway tunnels was below 50.00%. Correlation analysis results show that tunnel users’ demographic characteristics significantly affected their cognition of expressway tunnel escape methods. This study shows that tunnel users’ emergency escape knowledge regarding tunnels is relatively low. Corresponding countermeasures were proposed to guide policy decisions for enhancing tunnel fire safety.