To explore the status of teacher-student relationship of secondary school students, and its relation to their emotional intelligence and social problem-solving skills, a sample of 2172 students completed the questionnaires including Adolescents’ Emotional Intelligence Questionnaire, Inventory of Social Problem Solving Skills, and Inventory of Teacher-Student Relationships. The results indicated: (1) Secondary school students’ overall teacher-student relationship displayed significant differences in gender and grade: students in first grade had better relationship with their teachers than the second grade of junior and senior high school; boys scored significantly higher than girls in the aspect of conflict in teacher-student relationship, but girls scored significantly higher than boys in sense of satisfaction. (2) Emotional perception negatively predicted intimacy, and positively predicted conflict of teacher-student relationship. Moreover, emotional facilitation, emotional understanding and emotional regulation significantly predicted teacher-student relationship. In particular, emotional facilitation most strongly predicted intimacy, support and satisfaction, while emotional regulation had the strongest negative prediction to conflict of teacher-student relationship. (3) Social problem solving skills partly mediated the relation between emotional intelligence and teacher-student relationship of secondary school students.