Despite the increasing pace of technological change and digitalisation of workplaces, low-educated workers continue to participate in non-formal adult education (NFE) to a significantly lesser degree than do other workers. At the same time, low-educated workers also face many other barriers to participation. One key question related to their non-participation is what role the different types of perceived barriers play. Based on an earlier investigation, we have identified dispositional, situational, and institutional barriers to non-participation in NFE. The aim of the present two-step empirical research is to determine the structure (first step) and occurrence (second step) of these barriers in low-educated workers. For this purpose, we have used the specially developed research tool Non-Participation in Non-formal Education Questionnaire (NP-NFE-Q). Based on this validated tool, we have done a two-step empirical investigation on representative sample of low-educated workers from the Czech Republic that shows the strength of situational barriers related to the workplace, and distinguishes individual groups of non-participants through a cluster analysis. The results expand knowledge in the field of adult education and offer practical implications towards the higher participation of low-educated workers in NFE.