The relationship between material deprivation, economic poverty and education exclusion has been a focus of attention in numerous political and academic debates. Accordingly, the aim of this paper is to analyse the relationship between structural positions -- and material disadvantages -- and young people's educational trajectories (especially, educational exclusion and early school leaving processes), as well as the role of schooling institutions and subjective dispositions as mediating factors. The study, centred on a working-class city in Spain, draws on qualitative methods: semi-structured interviews with key informants (n = 26) and life-stories of young people in a situation of or at risk for Early school leaving (ESL, n = 25). Our results point to a complex, contextual, and non-deterministic relationship between structural positions and educational trajectories and to the key role played by schooling institutions and subjective dispositions as mediators of that relationship. Finally, we conclude this paper reflecting on the role of the State in reducing ESL-processes.