This study aimed to explore what factors affect teachers’ acceptance and instructional use of ICT in Chinese higher vocational colleges. Grounded in the modified UTAUT model, the current study investigated the direct and indirect effects of teachers’ performance expectancy, effort expectancy, external conditions, and behavioral intentions on using ICT in teaching. A total of 6087 teachers from 219 vocational colleges in 28 provinces in China participated in a large-scale survey. Structural equation modeling revealed that the teachers’ psychological perceptions (including performance expectancy, effort expectancy, and intention to use ICT technology) and the external support conditions (including professional development support, infrastructures, the climate of organizational reform and innovation, and teacher performance assessment mechanisms) significantly directly affect the use of ICT in Chinese higher vocational college teachers’ teaching practice. Moreover, this study confirmed the mediating role of teachers’ intention to use ICT in teaching in the relationship between teachers’ psychological perceptions and ICT instructional usage behavior. However, there were differences in the significance of these variables in the chain effect of teachers’ intention to use ICT. These findings expand our understanding of the factors influencing ICT use in teaching among VET teachers in China and thus provide practical implications for higher vocational college managers to promote teachers’ ICT teaching behaviors.