Little is known about the buffering role of social support among orphans living in Africa. This study examined (1) how perceived social support (PSS) varied across orphan‐related characteristics (e.g., orphan status, such as single, maternal or paternal, and their living environments, such as in child‐headed households, on the street, in an orphanage or in a foster home) and (2) the relative importance of sources of PSS (relatives/community/adults and peers) and functional social support (emotional/informational/instrumental and social) and its association with emotional well‐being and mental distress. The participants included 430 orphaned Rwandan children and youth aged between 10 and 25 years (Mean age = 17.74), of whom (n = 179, 41.6%) were females and (n = 251, 58.4%) were males. Result showed that children living in an orphanage exhibited a higher level of PSS from all sources of social support than did children in other living environments. A higher level of PSS from relatives, communities and adults was associated with high level of emotional well‐being, and only adult support was associated with low level of mental distress. Furthermore, the functional PSS indicated that emotional support and companionship support were equally important in their association with higher levels of emotional well‐being and lower levels of mental distress. The findings highlight the importance of having different sources of social support and their functions in relation to psychosocial well‐being.