Introduction: Mountaineering courses are exceptionally physically demanding outdoor activities, and wilderness solitude is a challenge that tests both the mind and body. Participants who choose this course should be guided by robust internal motivation and value recognition. We integrated the experience of wilderness solitude into our courses and used the Means-End Chain theory to explore changes in the experiential value of course participants. Methods: This study involved 26 students who took the mountain activities and environmental exploration course. They underwent three days and two nights of field practice and 12 hours of wilderness solitary experience without computers, communication, and consumer electronics products and equipment. In-depth semi-structured ladder interviews were conducted before and after the course. Encoded data was used to construct an implication matrix and a hierarchical value map for further analysis and discussion. Results: (1) The common values recognized throughout the course were self-realization, self-growth, physical and mental health, social support, and environmental ethics. (2) The wilderness solitude experience helped participants with self-reflection and personal growth, and the reflection process helped to change their thinking patterns, leading to a positive attitude towards life. (3) The wilderness solitude experience triggered a more profound sense of environmental ethics, strengthened attitudes and behaviors towards the environment, and positively impacted environmental protection. Conclusion: Experiencing solitude in the wilderness enhanced personal growth, expanded social relationships, and strengthened environmental awareness for participants in mountain activity courses. The value context of participation motivation can be explored through the Means-End Chain theory. This study's results can provide a reference for outdoor curriculum design and promotion marketing.