While previous research has shown that personality shapes social networks, we know very little about the relationship between these important psychological characteristics and the creation of social capital. In this article, we argue that personality shapes individuals’ ability to create social capital, and we predict positive associations between each of the Big Five personality traits and social capital. We tested our hypotheses using the Social Survey of the Networks of the Dutch, 2014, which contains data on about 1,069 respondents, including social capital and Big Five personality measures. Our findings showed that personality and social capital were related such that extraversion and openness predicted instrumental social capital, and extraversion, emotional stability, and agreeableness predicted expressive social capital. Conscientiousness benefited instrumental social capital when respondents were older or when social capital was accessed via weak ties. We discuss these findings in light of existing explanations of the creation of social capital.