The current study examined a multiple mediator model based on the control-value theory. A sample of 433 Chinese junior middle school students participated in questionnaires assessing teacher-student relationships (TSRs), academic emotions, academic value (AV), and academic self-efficacy (ASE). English test scores were collected as an indicator of students' English academic performance. The results indicated the following: (a) for academic enjoyment, the TSR has an effect on academic achievement through the chain intermediary of AV and ASE; (b) for academic relaxation, the TSR has an effect on English academic achievement through the single intermediary of academic relaxation and the chain intermediary of AV, ASE, and academic relaxation; (c) for academic anxiety, the TSR has an effect on English academic achievement through the single intermediary of AV, the single intermediary of academic anxiety, and the chain intermediary of AV, ASE, and academic anxiety; (d) for academic boredom, the TSR has an effect on English academic achievement through the single intermediary of academic boredom. These findings enrich the relevant research on the control-value theory and provide important insights for improving students' English academic achievement.