In this article, the motives for voluntary work and work values in higher education contexts are examined in a cross-border region in Central Eastern Europe. Our goal is to find out what kind of relationship exists between different types of volunteering and work values among young people. In the theoretical section, we deal with the definition of volunteering in the education system, the types of and motives for students' volunteering, and finally, the relationship between the work values and voluntary work of students. In the empirical section, we created cluster groups based on students' motives for volunteering, and we examined differences among countries. Then we revealed the factor structure of the work values of students and analyzed the relationship between cluster groups and factors with variance analysis. Five cluster groups were identified: "careerists with postmodern features," "unmotivated," "highly motivated," "volunteers in an anti-volunteering climate," and a "helping new type volunteers" group. There were only slight differences among countries, as most respondents are characterized by mixed motivations. An interesting result is that the most frequent group is "the volunteers in an anti-volunteering climate" in all the countries examined, especially in Ukraine, so the culture of volunteering is not popular enough in this region of Central Eastern Europe. Regarding the relationship between work values and volunteering, we have found that these two fields (work values and volunteering) are closely related.