While faculty to freshmen mentoring (FFM) has been shown to benefit freshmen, not all of them wish to engage in such a program when entering higher education. This questionnaire survey (N = 551) built on the theory of planned behavior to investigate the determinants of freshmen's intention to engage in a large-scale FFM program called POLLEM. Results showed that general factors were at work, as well as factors specific to mentoring and to FFM in particular. They revealed that freshmen's experiential attitude, descriptive norm, injunctive norm and perceived ability matter and highlighted key underlying beliefs (e.g. mentoring boosts self-esteem, shyness impedes engagement) as playing a major role. This study therefore confirmed the relevance of the TPB for understanding/studying the decision to engage in mentoring and for designing interventions likely to boost it.