This paper explores the premise that children in poverty are disadvantaged in their potential to learn by the extent and quality of their social networks and educational relationships. The research examines the quality and sustainability of educational relationships between children and adults in out-of-school activities. We build a theoretical argument to suggest that children with a greater number of successful, formal and informal educational relationships stand a better chance of success in terms of on-going learning and rewarding employment. The study probes how children act as agents in developing and maintaining educational relationships with adults and the constraints on the use of their own agency in negotiating more formal educational settings. It explores educational relationships out of school and compares and contrasts the educational relationships experienced by children in poverty with a matched sample of those in more affluent circumstances. In doing so, it illuminates the nature and scope of educational relationships in supporting children's engagement with learning; identify perceived gaps in their experiences and capture their explanations of the cause. Learning how to develop and sustain relationships, how to work with others, make use of, and build on other's expertise are vital in improving life chances and these are the skills much demanded by employers. This research contributes to the understanding of the relationships that support the learning of children in poverty and of the barriers that obstruct their development in school.