Following the organizational learning theory and the knowledge‐based view approach, this contribution aims to study the influence of entrepreneurial orientation and learning orientation on organizational learning, considering the latter as a mediating variable in the relationships between both antecedent cultural values and business performance. We also analyse the moderating role of organizational size on these previous relationships. The hypotheses proposed in our research model are tested on a sample of 140 Spanish industrial companies, applying variance‐based structural equation modelling: partial least squares. In order to assess the moderating effects of organizational size, we adopt a multi‐group approach using two subsamples with large firms and small and medium‐sized enterprises (SMEs). Our findings indicate that organizational learning partially mediates the relationship between entrepreneurial orientation and performance and fully mediates the link between learning orientation and performance. Likewise, the results reveal that the relationship established between entrepreneurial orientation and organizational learning is more intense for the group of large firms than for the group of SMEs. Moreover, the influence of learning orientation on organizational learning is greater in SMEs than in large firms.