This article introduces the concept of socio-connective trust, the synapse between the social structures and processes that underpin relationships in supportive care networks. Data from an ethnographic case study of 18 informal caregivers providing in-home care for people with life-limiting illness were analysed drawing on theoretical concepts from the work of Giddens and writings on social capital, as well as the construction of trust in the caregiving literature. While conceptions of trust were found to contribute to understanding supportive care relationships, they did not account for the dynamic nature of the availability and use of support networks. Instead, informal caregivers undertook ongoing reflexive negotiation of relationship boundaries in response to their own conception of the current situation and their perception of trust in their relationships with the various members of the support network. The concept of socio-connective trust describes the movement and flow of the flexible bonds that influence relationships among care networks and determine the type and range of support accessed by informal caregivers. Understanding the complexities of socio-connective trust in caregiving relationships will assist health and social care workers to mobilize relevant resources to support informal caregivers.