This paper examines educational segregation in the Brazilian city of Rio de Janeiro through the lens of a multifaceted centreperiphery relationship involving geographical, racial and historical dimensions. The paper first situates Brazilian racial inequalities historically, drawing on decolonial theory, before examining student enrolment patterns in Brazil's second-largest metropolis. Although Brazil is often held to be a racially integrated society, the analysis shows sharp racial and social divisions between a 'peripherally' oriented mass public school system, a 'centrally' oriented private sector, and selective public schools run by the federal government. The selective public sector is undergoing a period of transition, driven by affirmative action policies, and provoking tensions that are examined through the experiences of two politically-engaged teachers. The findings point to the importance of political mobilisation in effecting change and the need for further affirmative action policies, along with a revised funding model for public schooling.