This paper presents the results of a research that investigated the extent in which volunteering is present in the population of unemployed in Croatia (in Split-Dalmatia county), and in which way volunteering can be a useful way and measure for their faster and more productive (re)employment. Attitudes and perceptions of unemployed volunteers have been compared with those from non-volunteers, as well as unemployment records of those two populations. Finally, the potential of volunteering as a tool for faster and more productive employment of unemployed has been assessed.Strong evidence that volunteering helps to faster and more productive employment of unemployed has been found. Research showed that population of unemployed is very good target group to promote volunteering as the way to acquire new knowledge and skills. Unemployed see volunteering, among other, as a good vehicle to improve their employability and entry into the 'world of work'. Promotion of volunteering among unemployed should be seen as the activity that contributes not only to develop volunteering and increase individual and social benefits from volunteering itself, but as activity and tool to reduce unemployment, shorten unemployment duration for individuals, and increase productive utilisation of human capital.