Values are an important topic that has received significant scholarly attention from various academic disciplines. The theoretical framework used for individual values research is Schwartz’s value theory that defines ten basic values: power, achievement, hedonism, stimulation, self-direction, universalism, benevolence, tradition, conformity, and security. In order to better understand the motivational background of attitudes and behavior of Internet users, the paper explores the structure of their personal values. A large telephone survey in Croatia in 2016 was conducted on a nationally representative sample of 2,060 Internet users. Values were measured with the Short Schwartz’s Value Survey instrument. Internet users are grouped in different value-related groups with K-means cluster analysis. Furthermore, differences among those value-related groups of Internet users are examined with regard to their levels of social trust, computer anxiety, need for privacy online, online privacy concern and demographics. There were three mutually exclusive groups of Internet users found, namely: power-oriented group, self-centered group and self-transcendent group. Significant differences were found among those groups regarding social trust, expressed computer anxiety and need for privacy online. Demographic characteristics in terms of gender, age, education, income, and occupation explain the observed differences among the clusters of Internet users.