This study examined whether the effectiveness of virtual reality (VR) in science education could be enhanced by providing students with relevant information about VR’s usefulness before a virtual lesson. On the basis of expectancy–value theory, we manipulated students’ perceived usefulness of VR by using video priming before presenting a virtual biology lesson. We then assessed how the intervention affected students’ presence, interest in the virtual lesson, and learning achievement. Additionally, we tested the relationships between presence and learning outcomes. A sample of 196 students in Grade 10 was randomly assigned to a learning-usefulness condition, a daily-life-usefulness condition, or a control condition (no priming intervention) in VR. The results showed that students in both experimental conditions perceived VR as significantly more useful for learning and had greater learning achievement than those in the control condition. In addition, students in the daily-life-usefulness condition experienced less presence than those in the control condition, but there was no difference between the learning-usefulness condition and the control condition in this regard. However, the intervention had no effect on students’ interest in the virtual biology lesson. Moreover, students in the two experimental conditions did not differ from each other on any of the outcomes we considered. Furthermore, the results revealed that students’ presence was positively associated with their interest in the virtual lesson but was not related to their learning achievement when the intervention’s effects were controlled for. These findings suggest that students’ awareness of VR’s usefulness could be a factor in VR’s effectiveness.