Grounded in Self-Determination Theory (SDT), this study aims to examine whether the effects of a hybrid Sport Education (SE)/Teaching Games for Understanding (TGfU) a volleyball teaching unit were equally effective on a set of SDT-related variables according to students’ initial motivations. A pre-experimental pre-/post-test design without a control group was conducted in a volleyball teaching unit in Physical Education. A final sample of 49 students (M = 15.50, SD = 0.57), in their fourth year of secondary education, participated in a hybrid SE/TGfU volleyball teaching unit composed of 10 lessons. The structure of this unit was designed according to the characteristics of an SE model, while learning tasks were designed using the TGfU model. Different validated questionnaires on basic psychological need (BPN) support and satisfaction, novelty and variety satisfaction, motivation, and intention to be physically active were completed by students. Three different profiles with different Relative Autonomy Index (RAI) levels (i.e., “high”, “moderate”, and “low”) were identified through cluster analysis before starting the intervention. Although the SE/TGfU of a volleyball teaching unit were effective in improving SDT-related variables in the three profiles identified, a large effect size was observed in profiles with a “moderate” or “low” RAI. The hybridization of these two pedagogical models could be a tool for improving motivational outcomes in students who are less motivated in Physical Education lessons.