Twenty-eight people (30–70 years old, 12 men, 16 women, artists and non-artists) participated in a comparative neuroaesthetic study in the conditions of real-life visit to M. Vrubel mono-exhibition (Russian Museum, St. Petersburg). During the visit to the exhibition (usually lasted for around 60 min), EEG of participants was recorded. The subjects were looking at the paintings for 30 seconds to 3 min and evaluated the subjective aesthetic “attractiveness” of the paintings by a series of button presses (from 1 to 10). Were analyzed EEG spectral power in the α1 (8–10 Hz)-, α2 (10–13 Hz)-, β1 (13–18 Hz)-, β2 (13–30 Hz)-frequency bands during viewing the most famous Vrubel paintings (“Bogatyr”, “Swan Princess”, “Swan”, “Sitting Demon”, “Flying Demon”, “Pan”, etc.) and event-related EEG synchronization/desynchronization in relation to the subjective emotional and aesthetic evaluation of these paintings. Professional artists showed lower spectral power values in α1 (leads F3, C3, T4, Pz) and α2 (F3, Fz, F4, C3, Cz, C4, P3, Pz, P4)-frequency bands in frontal, central, and parietal regions. The artists were also found to have lower power values in β1,2-frequency bands in frontal (F3, F4, C3) regions and higher power values in occipital (O1, O2 – β1, β2) and posterior temporal (β2) cortical regions compared to the group of subjects with no special artistic education. Moreover, artists decision-making about the high emotional-aesthetic attractiveness of paintings was accompanied by an increase in event-related EEG synchronization for 11.5–27 Hz in frontal and central cortical areas over 580–360 ms before giving the response, compared to non-artists, whereas low emotional-aesthetic evaluation was characterized by 9–27 Hz EEG desynchronization, which started 60 ms before the giving the response and lasted up to 440 ms after it, in the posterior temporal and parietal regions. The differences in frontal cortical areas may indicate a higher engagement of the reward system during the perception of aesthetically pleasing paintings, and the differences in parietal and posterior temporal areas may indicate a continuing visual synthesis (more sustained visual attention) during the perception of subjectively less attractive paintings in artists compared to non-artists.