Peer mentoring in the dawn of new educational paradigms harnesses the act of becoming an educationist to facilitating learning in a peer mentoring practice. This study explored the opportunities of an emancipatory approach to teaching and learning under the thrust of learning together, learning deeper through the indulgence of little teachers under the peer mentoring scheme of learning. Employing the senior secondary education students (as little teachers), who came from their Student Teaching program from the Department of Education, and the junior secondary education students (as mentees), who enrolled in their Teaching Science in the Secondary Schools under the qualitative research design and phenomenology as point of inquiry, the following were found: Mentors in the mentoring process need to be approachable and accommodating; Mentees in the mentoring process need to be responsible with their learning task coupled with learning initiative; Enjoyable learning encounters, collaborative learning sessions, open and barrier-free communication, and close and rigid supervision through spoon feeding, modelling, and feedback are some of the perceived characteristics of an effective mentoring program; and Readiness of both mentors and mentees hinder the efficacy of the mentoring program. Owing to the results of the study, it is recommended that a formal mentoring program in the College of Teacher Education be institutionalized for it spurs extensive learning.