Drawing on research conducted as part of a UN sabbatical leave programme, this article seeks to challenge a long-standing understanding of human rights and peace mediation as two distinct and often competing areas of work and expertise at opposite ends. By illustrating how human rights analysis and actors have directly contributed to and facilitated mediation efforts, the article demonstrates the inherent problem-solving nature of human rights by putting a spotlight on their role in supporting peace-making efforts by the UN and other entities. The article is based on eight in-depth case studies—from Palestine in 1948 to Colombia in 2016—and close to 60 interviews with present and former senior UN officials, representatives of non-official intermediaries and other experts engaged in mediation and human rights. With a view to better and more consistently applying the inherent potential of human rights in the political work of mediators, it demonstrates how human rights in fact stand ‘at the heart of mediation’ and breaks a prevailing narrow understanding of rights concerned primarily with criminal accountability. In so doing, the article not only fills a gap in academic literature but aims to trigger debate among practitioners and researchers on how human rights experts and mediators can learn from each other’s comparative approaches with a view to designing more sustainable and legitimate peace processes.