<p>In the past 50 years, the level of educational attainment of the population of the United States (US) has increased. However, approximately 50 per cent of young adults still enter the workforce after high school instead of pursuing postsecondary education. Given that postsecondary education is associated with multiple personal and social benefits in adulthood, it is vital to explore ways of ensuring that working adults have opportunities to access postsecondary education so that they continue to develop their skills and competencies, and are able to meet labour market needs. This study examines the relationship between the workplace learning experience and postsecondary access of working adults who entered the workforce with a high school diploma. The authors’ analysis of the US data from the Programme for the International Assessment of Adult Competencies (PIAAC) indicates that working adults’ structured on-the-job training experience is positively associated with their access to sub-baccalaureate and bachelor’s degree programmes. In contrast, the data suggest that informal learning in the workplace does not significantly enhance postsecondary access. The study discusses the implications of these findings, highlighting the potential benefits of structured learning in the workplace.</p>