Relational capital is a critical asset in the knowledge economy. It refers to the sum of relations an entrepreneur establishes with the external environment and stakeholders aimed to generate business value. Relational capital is particularly relevant for start-ups and for women entrepreneurs. This chapter analyzes the role of relational capital in women in entrepreneurship based on a start-up case associated with a regional Imprenderò program to support entrepreneurs during 2011–2012, coinciding with the financial crisis. We assess the outcome of the program to understand the challenge that entrepreneurs in general and women in particular faced. A specific case is analyzed using the CAOS model of micro-entrepreneurship by Paoloni (2011) to assess the benefits of relational capital (RC) in entrepreneurship. The study contributes to the debate regarding links between relational capital and female start-ups and understanding how they affect the wellbeing of women in entrepreneurship.