Although mentoring has become increasingly popular within UK higher education, there is little evaluative research. The current longitudinal study aimed to evaluate the usage of a peer mentoring scheme during a first semester at university amongst 124 students. Results indicate that during the first week at university the majority accessed the scheme but this then diminished by 10 weeks. There were strong positive correlations among contact, satisfaction and perceived mentor social support. Additionally, expectations of mentoring mediated the relationship between contact time and satisfaction. Correlations with student well-being and intention to withdraw, however, indicated that students reporting high levels of mentor support were worse off than those reporting less support. Students wanting more support from mentors were significantly lower on levels of integration and well-being. Findings suggest a potentially vulnerable group of students who access and use the mentoring scheme because of the problems they are experiencing.