Surveys that examine the perceptions of employees regarding lifelong learning in Greece reveal that employees have a positive attitude towards education and also indicate that about 70% of the working population showed intention to participate in some form of continuing education. However, the participation rates of Greek employees in educational programs are below the European average. At this point, it is worth noting that little is known regarding the barriers that prevent them from participating. In this light, the present study is the first attempt to investigate both individual barriers and barrier categories of employees’ participation in Greece. Survey data were collected using a questionnaire. The results of the present study revealed four categories of barriers. Of these, situational barriers gathered the highest average, followed by <italic>institutional: state/institute barriers and, institutional: working environment and, to a lesser extent, dispositional barriers. In particular, the three main barriers faced by employees were the “lack of time due to work obligations”, the “participation cost”, and the “lack of time due to taking care of children.” In addition, the categories of barriers were found to be related to three of the four demographic variables examined: gender, employment status, and occupation, which were independent of age.