This work has been carried out to support the investigation of the electroencephalogram (EEG) Fourier power spectral, coherence, and detrended fluctuation characteristics during performance of mental tasks. To this aim, the presented dataset contains International 10/20 system EEG recordings from subjects under mental cognitive workload (performing mental serial subtraction) and the corresponding reference background EEGs. Based on the subtraction task performance (number of subtractions and accuracy of the result), the subjects were divided into good counters and bad counters (for whom the mental task required excessive efforts). The data was recorded from 36 healthy volunteers of matched age, all of whom are students of Educational and Scientific Centre “Institute of Biology and Medicine”, National Taras Shevchenko University of Kyiv (Ukraine); the recordings are available through Physiobank platform. The dataset can be used by the neuroscience research community studying brain dynamics during cognitive workload.