For early emerging adults with serious mental health conditions, vocational services with peer mentors are a promising adaptation of adult system evidence-based practices. Peer mentors were added to the Individual Placement and Support model of supported employment for 17- to 20-year-olds receiving residential and psychiatric care. To explore the feasibility of vocational peer mentors, open-ended satisfaction surveys and the Working Alliance Inventory were administered to mentees at 12 months. Thematic analysis of surveys reveals the importance of peer mentor authenticity, flexibility, and being a graduate of the mental health program where vocational services were based. Valued relational processes include the act of talking in the community, feeling understood, and forming a bond with peer mentors. Mentees with positive peer mentoring experiences reported stronger working alliances. This study sheds light onto near-age mentoring relational processes for this population, which can inform future research of mentoring processes and intervention design.