Social capital, derived from the individual embeddedness in a net of personal relationships that gives access to a pool of potential resources, is crucial to understand how some people experience a higher risk to fall into social exclusion. In this paper, we relate some compositional and structural factors of egocentered networks to some measures about economic deprivation and social exclusion. We aim to examine to what extent the relational fabric prevent individuals from suffering material deprivation. Different dimensions are considered to explain the degree of social exclusion: ego’s psychological features, ego’s sociodemographic characteristics and ego’s social capital. Social capital is measured both in terms of expressive and instrumental support and takes into account network size, density, and mean prestige. Structural indicators are just available for expressive, core discussion networks up to five elicited persons. Special attention is paid to the effect of inherited capital versus achieved capital. Data from the Spanish General Social Survey 2013 were used, and regression models were applied to the nationally highly representative sample of adult population. Regressions show interesting results both at the meso level and at the individual level. Regarding network structure, resources and composition, there exist an association between social exclusion and lower prestige of achieved relationships, fewer resources for obtaining economic or medical help (but more resources for caring children) and smaller networks of expressive support. Although Spain is a familistic society, results confirm that achieved social capital is more important than ascribed one to be socially integrated. This means that, although the country has a strong economic inequality, social mobility is possible and the socially excluded have options to escape from this situation.