Purpose: Using Butler’s teacher achievement goal orientation as a conceptual framework, we developed this study to validate a teachers’ achievement goal instrument for teaching physical education. Methods: A sample of 322 Chinese physical education teachers participated in this study and completed measures of achievement goal orientations and job satisfaction for teaching physical education. Results: An exploratory factor analysis provided preliminary support with the instrument comprising four types of teachers’ orientation: mastery, ability-approach, ability-avoidance, and work-avoidance goals. A confirmatory factor analysis and multi-step invariance tests further corroborated the four-factor construct with acceptable reliabilities. Its predictive validity was also confirmed by the associations between job satisfaction and mastery goals and ability-approach goals. Discussion/Conclusion: Overall, the findings lend evidence to the conceptual validation of the structure of teachers’ goal orientations. It is suggested that physical education teachers’ individual differences in construing success be considered and instructionally addressed during teaching and learning.