With the deep integration of ICT into education and teaching, the effect of technology acceptance on students’ self-directed learning has been one of the key concerns in the education field. This study examines the relationship between technology acceptance and self-directed learning and the mediating role played by positive emotions and technological self-efficacy in a sample of 501 middle school students in eastern China. The results show that: (1) positive emotions mediate the relationship between technology acceptance and self-directed learning; (2) technological self-efficacy also mediates the relationship between technology acceptance and self-directed learning; (3) positive emotions and technological self-efficacy play a mediating role between technology acceptance and self-directed learning. The findings not only reveal the mediating role of positive emotions and technological self-efficacy between technology acceptance and self-directed learning but are also valuable for Chinese teachers to guide middle school students to engage in self-directed learning with the help of technology.