Mentoring programmes designed to support women in overcoming barriers in their career advancement are popular devices within gender mainstreaming strategies in academic and scientific environments. Recently, gender scholars have been developing a critical approach to mentoring schemes according to the gendered-organisations theoretical framework. Schemes focused on women rather than on the gendered structure of academic institutions would induce adaptive behaviours, while the goal should be to trigger transformative practices towards gender equality in academia. The Italian University of Naples Federico II (UNINA) Mentoring Pilot Programme was inspired by this approach. It was embedded within the Gender Equality Action Plan implemented by GENOVATE@UNINA and supported by other initiatives aimed at increasing gender awareness and promoting women researchers’ networking toward structural change in academia. This chapter synthesises the main results of the programme and monitors its implementation at UNINA. It focuses on participant female researchers’ careers as a lens for studying the gendered structure of Italian academia.