Social exclusion is considered critical for understanding poverty, livelihoods, inequality and political participation in rural India. Studies show how exclusion is produced through relations of power associated with gender, caste, religion and ethnicity. Studies also document how people confront their exclusion. We use insights from these studies – alongside science and technology studies – and rely on life history narratives of ‘excluded’ people from rural Tamil Nadu, to develop a new approach to agency as constituted by two contrasting ways of relating: control and care. These ways of relating are at once social and material. They entangle humans with each other and with material worlds of nature and technology, while being mediated by structures such as social norms and cultural values. Relations of control play a central role in constituting exclusionary forms of agency. In contrast, relations of care are central to the agency of resistance against exclusion and of livelihood-building by the ‘excluded’. Relations can be transformed through agency in uncertain ways that are highly sensitive to trans-local contexts. We offer examples of policy-relevant questions that our approach can help to address for apprehending social exclusion in rural India and elsewhere.