There is little academic research in relation to mentoring, learning and women, particularly in the male-dominated organizational context of the UK Police force. Currently, there is a Home Office drive to address inequality within the UK Police with a number of initiatives proposed including mentoring interventions, flexible working arrangements and positive-action recruitment initiatives. The purpose of this study is to investigate what policewomen mentees and mentors perceive they are learning through formal mentoring over time and how this makes a difference for them in the workplace. This will provide insights into whether Government investment in formal mentoring is the right intervention to help create a more gender-reflective, more equal workforce, in the Police. This study takes a critical realist position and an interpretivist theoretical perspective investigating a single case study organization. Key themes, spread across the four phases of the mentoring lifecycle were explored through 68 semi-structured interviews and four focus groups. Key findings are uncovered in relation to learning outcomes for these policewomen, both as mentees and mentors. It was found that mentoring added value across all four learning domains (cognitive, skills, affective-related and social networks) and that the largest number of responses over time, were in relation to the affective-related domain, particularly building self-confidence. These findings are significant as they demonstrate that formal mentoring programmes can support and empower women within the specific workplace of the UK Police. In conclusion, if women are being precluded from breaking the “glass labyrinth” because of lack of knowledge, opportunity and networks to progress within this context, then mentoring could be part of this solution. If the masculine organizational culture is also creating prejudice and obstacles for women in the workplace (the “concrete floor”), then mentoring might be one way towards breaking down these barriers. In addition, if all (or some) of these factors are contributing to women’s lower self-confidence levels and the “sticky floor” syndrome, then again the findings suggest that mentoring may be part of the solution towards empowering women beyond their current role. It is hoped that these insights will impact the emphasis put on the various Home Office recommendations and the initiatives offered by different Police forces. It is also hoped that these insights will have implications for other organizations that are considering investing in mentoring interventions, for similar groups or beyond. This article is published as part of a collection on the role of women in management and the workplace.