The study looked back on the one-year experience of the first group of peer mentors of a university at northern Taiwan. Twelve peer mentors (six males and six females; with an average age of 21.45) took part in the study. A qualitative phenomenological approach and in-depth interviews were adopted. The results showed that participants deemed the peer mentoring experience as a unique interpersonal relationship experience and the experience helped them develop in the areas of self-awareness, responsibility, sense of mission, interpersonal interaction, resource utilization, leadership, management, coaching, problem-solving, and self-identity. It is suggested that universities leveraged the peer mentoring system to assist students, especially freshmen, to adapt to university life. Peer mentors should undertake pre-training as well as on-the-job training with the help of professionals with different expertise.