This article uses data from the PIAAC (Programme for the International Assessment of Adult Competences) Background Questionnaire to describe conditions related to informal learning (IL) in the workplace and opportunities to learn informally in organizations in Spain. PIAAC data indicate that in Spain, informal learning processes in organizations are a common, everyday practice. However, some differences have been found in the intensity of this learning by gender, the position that the employee occupies and the business sector in which the organization is framed. This study opens some future avenues to develop further knowledge about IL mechanisms and practices in the workplace, as a strategy to help towards the development of people and organizations.