Social capital is a term that has evolved within the social sciences, and has been presented as a mediating factor in how people experience the social environment. In 2008 and 2009 we conducted one-to-one interviews with 61 people experiencing homelessness in an effort to investigate the concept of "pathways" from homelessness. Our findings show that social capital was not just about making positive friends or improving social relationships. Instead, personal issues of identity, self-esteem, and individualization were contributing factors to developing social capital; and social service agency practices could contribute to how these are experienced. Further areas of research are discussed along with the application of research findings to other vulnerable populations.