Using self-determination theory (SDT), this study simultaneously investigated the relationships between intrinsic motivation, psychological factors (sport enjoyment, social self-efficacy), and sociorelational factors (perceived coaching behaviors) by subsequently testing whether psychological factors mediate the relationships between social-relational factors and intrinsic motivation. One hundred and twentyseven early adolescent females from several teams of the Italian Volleyball Society completed a self-report questionnaire. Results showed that female athletes’ intrinsic motivation was associated with a) sport enjoyment and b) perceived coaching behaviors (e.g., training and instruction, social support). Second, results showed that training-and-instruction coaches’ leadership style affected intrinsic motivation via the females’ enjoyment in sport. This study provided further insights into unknown associations among psychological, sociorelational factors and intrinsic motivation, highlighting the innovative role of sport enjoyment as a key factor for sustaining intrinsic motivation. Original and useful behavioral suggestions will be given to the coaches in order to sustain female athletes’ sport enjoyment and their intrinsic motivation.