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The aim of this study was to identify the angular position differences between high (HP) and low (LP) men’s volleyball performers at the instant of take-off and ball impact. Ten skilled collegiate men’s volleyball players were recruited from the university club team. All joint angular positions were obtained via 3D motion analysis. Results indicated that the HP players had greater normalized CoM (p < 0.004) and reach height (p < 0.004) at the instant of take-off and ball impact than the LP players, respectively. At the instant of take-off, HP players had a greater extension at hips, right knee, right elbow, left shoulder (flexion), and right shoulder (abduction) than LP players (p < 0.004). At the instant of ball impact, the HP players demonstrated greater right elbow extension, right ankle plantar flexion, right shoulder abduction, and smaller left shoulder flexion than the LP players (p < 0.004).