This study investigated learning activities and associated quality of experience of students with different levels of perceived academic self-efficacy. Two groups were formed out of 130 Italian adolescents (age 15-19), one with high and one with low academic self-efficacy beliefs (31 and 32 participants, respectively). Students provided valuation of academic pursuits and aspirations, and were monitored for one week with experience sampling method (ESM). Attention was paid to the association of learning activities with optimal experience, characterized by high perceived environmental challenges matched by high personal skills, involvement, concentration and intrinsic reward. High self-efficacy students reported higher academic aspirations and pursuits than low self-efficacy students. They also spent more time in homework, and primarily associated learning activities with optimal experience. Results have educational implications in fostering motivation and enjoyment in learning. They also provide empirical support for the combination of self-efficacy beliefs and quality of experience in motivational research.