Classification of electroencephalogram (EEG) signal is important in mental decoding for brain-computer interfaces (BCI). We introduced a feature extraction approach based on frequency domain analysis to improve the classification performance on different mental tasks using single-channel EEG. This biologically inspired method extracts the most discriminative spectral features from power spectral densities (PSDs) of the EEG signals. We applied our method on a dataset of six subjects who performed five different imagination tasks: (i) resting state, (ii) mental arithmetic, (iii) imagination of left hand movement, (iv) imagination of right hand movement, and (v) imagination of letter “A.” Pairwise and multiclass classifications were performed in single EEG channel using Linear Discriminant Analysis and Support Vector Machines. Our method produced results (mean classification accuracy of 83.06% for binary classification and 91.85% for multiclassification) that are on par with the state-of-the-art methods, using single-channel EEG with low computational cost. Among all task pairs, mental arithmetic versus letter imagination yielded the best result (mean classification accuracy of 90.29%), indicating that this task pair could be the most suitable pair for a binary class BCI. This study contributes to the development of single-channel BCI, as well as finding the best task pair for user defined applications.