The transformation toward a sustainable economy is considered one of the most effective measures to accelerate the achievement of the United Nations’ Sustainable Development Goals for 2030. Sustainable entrepreneurs contribute to this transformation by identifying and exploiting business opportunities based on sustainability challenges such as biodiversity loss. Recognizing a business opportunity to achieve sustainable development characterizes the beginning of the sustainable entrepreneurial process. Sustainable entrepreneurship education (SEE) aims to foster skills, knowledge, and attitudes to accomplish tasks within this complex process. Role models are a common pedagogical instrument in educational settings, such as SEE at higher education institutions, where sustainable entrepreneurs are integrated into the curriculum to enhance learning outcomes. Given the limited research on SEE for secondary education, an exploratory study is conducted to investigate the effects of sustainable entrepreneurial role models on opportunity recognition for sustainable development. A total of 136 secondary school students participated in a program that guided them through the first steps of the sustainable entrepreneurial process. A total of 68 students were non-randomly assigned to sustainable entrepreneurial role models, providing support and feedback. During the program, groups of 3–5 students generated opportunity ideas (n = 35) for sustainable development. The quality of the opportunity ideas is explored by a qualitative content analysis. The obtained data is further analyzed for statistical group differences. The findings indicate the potential positive effects of sustainable entrepreneurial role models on idea generation for sustainable development. The results can advise educators and researchers on the design and investigation of SEE for secondary education.