A bulk of research has shown strong relationships between metacognition, creative thinking, autonomy support, and self-efficacy among teachers. However, we could not find research with a large sample of teachers exploring the mediating effects of creative thinking and metacognition on the relationship between autonomy support and self-efficacy. A need for a novel structural equation model (Covariance-based) underlying psychological rationality of said relationships was deemed actual. To that end, firstly the effects of teachers’ autonomy support (opportunity and decision-making) on teachers’ creative thinking, metacognition, and self-efficacy were tested. Then, the mediating effects of metacognition and creative thinking on the relationship between teachers’ autonomy support and teachers’ self-efficacy were explored. A simple random-sampling method was utilized to gather 787 teachers’ data. The results revealed that decision-making and autonomy opportunity predicted creative thinking, metacognition, and self-efficacy positively and meaningfully. Subsequently, creative thinking as well as metacognition had mediating effects on the effects of autonomy opportunity and decision-making on self-efficacy. In closing, for boosting teachers’ skills in autonomy support and self-efficacy, attention should be given to fostering their creative thinking as well as metacognition. The study provides implications and suggestions for research on school psychology and improvement.