One of the current trends in the world is formation of knowledge-based economies. A significant role in this process plays continuous vocational education and training of employees of enterprises as the main economic actors. The results of correlation analysis presented in the paper confirm the importance of on-the-job training and its interconnections with development of knowledge-based economy, competitiveness of the country and its economic growth. Considering Association Agreement between Ukraine and the European Union it is advisable to pay special attention to the peculiarities of vocational education and training in EU Member States. The complex study of the relationship between lifelong learning, on-the-job training, employment, development of the knowledge economy, economic growth and competitiveness within each country allows to divide the countries into two groups. This division was implemented according to correlation ties between the selected indicators. Taking into account the limited amount of funds spent on vocational education and training of employees at Ukrainian enterprises it is suggested to focus on creating organisational conditions for stimulating the development of self-education and professional self-improvement of employees. The establishment of the systems of organisational knowledge at enterprises is considered as the foundation for the development of such conditions.