Introduction: In the Baccalaureate, the exact and experimental science subjects demand the development of scientific competence, which in turn requires mastery of theoretical knowledge and practical knowledge, but also motivation and sustained effort for greater involvement and academic performance. Hence the relevance of knowing the motivational diversity that guides students to get involved (or not) in the learning of science, as well as the strategies necessary for them to persevere in achieving their goals, based on their own interests. The objective of this research was to analyze the motivational profiles of students and assess the possible relationships with volitional strategies and academic performance in experimental and exact science subjects at the Upper Middle Level. Method: The present study was carried out using a cross-sectional non-experimental quantitative design. 204 students from four high schools participated, aged between 16 and 18, who answered the Volitional Strategies Inventory (AVSI) and the Academic Goals Questionnaire (CMA), previously validated. Results: The results showed that the differentiated use of volitional strategies is related to the motivational profile of the students. Volitional self-efficacy control strategies are significantly related to academic performance. Discussion and Conclusions: This work shows the need to promote motivational and emotional strategies, in addition to cognitive ones, for better learning at the Upper Middle Level. Likewise, it is important to consider including in the curriculum the strengthening of volitional strategies so that students persist in the face of difficulties and remain motivated to achieve their academic goals.