Pedagogical content knowledge (PCK) has particular relevance for understanding the factors that contribute to high-quality teaching behaviors. This study sought to explore the relationship between teachers' PCK and students' opportunities related to learning outcomes in primary school physical education (PE), during ball game instruction. Data were collected from five female, primary PE specialist teachers and 125 students from the participating teachers' classes. Teacher PCK aligned with higher-level curriculum/developmental outcomes, greater student enjoyment and engagement, and more effective feedback for students. This research highlights the importance of PCK in accessing students' opportunities related to learning outcomes and student learning. (Contains 3 figures.)