This article presents empirical results from a study (2015–2018) on young people leaving care in Luxembourg. A special focus deals with the processes of transitioning from care to work. Education appears to be crucial for a successful transition, as it determines life chances, such as labour market chances, but so far inequality studies have neither researched transitions from care nor have the theoretical concepts developed in inequality research been used to understand the situation of care leavers. They might help to explain the different mechanisms behind the disadvantages of students in foster and residential care and their educational attainment. This paper thus attempts to theorise leaving care from an inequality perspective and the interdependencies with concepts of relational agency, taking into account the heterogeneity among care leavers, their trajectories and achievements (see also Gobel, Hadjar, Karl, Peters, & Jager, 2020). The main objective of our analysis is to investigate how agency is achieved in the transition from school to work among care leavers, taking into consideration institutional pathways (continuities and discontinuities) in the care and the educational system.