Several previous studies have emphasized the importance of situating students in authentic learning or problem-solving contexts to enhance their learning performances. However, some challenges of situated learning have been stated, such as the lack of effective learning support or concrete objective design to improve students' learning engagement, problem-solving competences and their active thinking. In this study, a mobile technology-supported experiential learning system was developed to improve students' problem-solving competences as well as their learning performances, attitudes and collective efficacy. Moreover, an experiment was conducted on an environmental science course in an elementary school to compare the effects of this method with those of the conventional situated mobile learning approach on students' learning effectiveness. The experimental results display that the implemented approach can significantly enhance students' learning achievements, environmental attitudes and collective efficacy; furthermore, the students who learned with the implemented approach showed higher problem-solving competence than those who learned with the conventional situated mobile learning approach, implying a noticeable reference for conducting experiential learning activities in environmental science education. Furthermore, the promotion of students' active thinking in the mobile technology-supported experiential learning is discussed.