This study focuses on two significant factors shaping university students’ perception of environmental sustainability. Those are (a) personal values, measured by the Portrait Values Questionnaire (PVQ) and (b) the usage of and proficiency in information technology. Personal values have been widely used to analyze individual perspectives toward various issues, including environmental ones. As contemporary social arrangements include significant influences from social networks and mobile phone usage, overall engagement with technology becomes an essential factor affecting university student attitudes and behaviors. While the individual impact of those factors can be found in the extant literature, we look into their interaction concerning university student pro-environmental attitudes, measured by the Revised NEP (New Ecological Paradigm) Scale, and their environmental self-efficacy. Our sample comes from the population of undergraduate business and economics students from Central and Southeast Europe, specifically Slovenia, Croatia, Bosnia and Herzegovina, Serbia, and Montenegro. We discuss our findings in the context of previous studies from the same regions and consider the unique socio-economic factors. The research results address Sustainable Development Goals 4 (quality education), 12 (responsible consumption and production), and 13 (climate action) by analyzing the factors contributing to university student pro-environmental attitudes and their self-efficacy in the context of their information technology usage and proficiency.