The implementation of digital educational environment (DEE) in higher education is a complex and multifaceted process, often accompanied by opposition. The opposition may be due to various reasons, among which psychological barriers can be mentioned, for example, negative experiences in educational activity, personality traits that prevent DEE acceptance, an insufficient level of behavioral self-regulation. The identification of such barriers by university students was the main aim of present research. Using a sample of students from various universities (N=1059, age 22.3 ± 7.1 years), the following indicators were measured: attitude towards educational activity (Activity-Related Experiences Assessment technique); the resources of self-regulation (Self-Activation and the Style of Behavior Self-regulation questionnaires); personality traits (Big Five Inventory-2), and the attitude towards learning in DEE (AUDEE Scale). Cluster analysis (k-means method) allowed to identify two contrasting groups of students, differing in their assessments of the university DEE: acceptance group and resistance group. The selected groups differ in agreeableness and conscientiousness, and both of these qualities are higher in the group that has positive attitude towards learning in DEE. Acceptance group also has a higher level of self-activation and self-regulation: its members better plan goals, program their actions and model significant conditions for achieving goals. Students from resistance group make more efforts in learning activities with less pleasure, they are characterized by such experiences as meaninglessness and emptiness (void). At the same time, psychological barriers are of transient nature, and students are able to overcome them over time with appropriate support.