Web 2.0-based learning enables collaborative learning and knowledge sharing and makes an important contribution to student learning. This study extended the original Technology Acceptance Model (TAM) by considering the effects of tool literacy, metacognitive self-regulation, subjective norm, facilitating conditions, and institutional support to understand pre-service teachers' intentions to use Web 2.0 technology in their courses. The sample data of 318 responses were from pre-service teachers. Structural equation modeling results showed a good fit for the extended model, indicating that metacognitive self-regulation and subjective norm had a significant influence on perceived ease of use and perceived usefulness, while institutional support and enabling conditions were not significantly associated with them. In addition, perceived ease of use and perceived usefulness influenced attitude, which in turn had a significant effect on intention. Furthermore, perceived ease of use, perceived usefulness, and attitude acted as significant mediators of behavioral intention. The indirect effect of perceived ease of use on perceived usefulness and attitude, and the indirect effect of perceived usefulness on attitude were also significant. Overall, the current study helps researchers and practitioners better understand future teachers' intentions to use Web 2.0 technologies in their courses.