The current educational model for the European Higher Education Area (EHEA), demands a greater involvement on the behalf of students in all aspects of their education. In this respect, peer mentorship not only provides effective orientation for newly admitted students, a key element of quality in education, but also the active participation of students mentors, leading to the development of a wide range of skills in both mentor and mentee students. From a research-action perspective, this article describes a program of peer mentoring, in which the student interaction taking place leads to wide-ranging knowledge acquisition (knowledge and know how) for both participants. Within the sphere of mathematics, the program was developed with the aim of developing general skills, as well as the specific objective of improving competence in mathematics. In the results obtained, the profile and educational development of the student mentor, together with the study of the needs of first year students, from the perspective of teachers and students, were especially relevant. The conclusions and recommendations from this study may constitute a good basis upon which future peer mentorship programs may be developed as an approach that is very much in line with the EHEA and of great educational value.