The development of the Internet contributes to the activity of education volunteers who disseminate a variety of information on the Web. This study is limited to virtual volunteers who share useful knowledge in cyberspace. Although the issues of volunteering are covered quite widely in psychological science, the volitional mechanisms that encourage online educational activities have been poorly studied. The leading role in the deployment of such prosocial behavior is played by a specific value-orientation system. The purpose of this research is to identify and describe the systems of values and value orientations of online educators, namely representatives of the expert core of the online encyclopedia “Wikipedia” (N = 96) and the question-answer (QA) online project “Otvety” (N = 47). The study is based on the value-specific (SVS, PVQ) methodology developed by Sh. Schwartz and adapted by V.N. Karandashev; the participants belong to the abovementioned expert core groups of online education volunteers. The results reveal their relatively homogeneous set of values, which is developing into an altruistic meta-orientation towards autonomously given and situationally different dissemination of knowledge aimed at providing information (as a public utility) and regulated by self-transcendence and openness to changes. Intersubjective (in terms of normative ideals and individual priorities) and intergroup (in terms of communities) value-related comparison of the study participants - Wikipedia authors and QA “Otvety” service experts - optionally show that the Wikipedians are more inclined to avoid saturated social relationships (being socially inert), however, are much more hedonistic about life than the QA-experts. At the same time, both groups are brought together as close as possible by the radical condemnation of any factors that interfere with social harmony and limit the freedom to manifest oneself as a person. Based on the obtained results, it can be concluded that further understanding of the personal and group characteristics of education volunteers can expand the scope of education; therefore, in subsequent studies, it is proposed to use successive psychodiagnostic methods that measure value specificity in a psychosocial context.