A number of recent studies have demonstrated that near-infrared spectroscopy (NIRS) is a promising neuroimaging modality for brain-computer interfaces (BCIs). So far, most NIRS-based BCI studies have focused on enhancing the accuracy of the classification of different mental tasks. In the present study, we evaluated the performances of a variety of mental task combinations in order to determine the mental task pairs that are best suited for customized NIRS-based BCIs. To this end, we recorded event-related hemodynamic responses while seven participants performed eight different mental tasks. Classification accuracies were then estimated for all possible pairs of the eight mental tasks (). Based on this analysis, mental task combinations with relatively high classification accuracies frequently included the following three mental tasks: “mental multiplication,” “mental rotation,” and “right-hand motor imagery.” Specifically, mental task combinations consisting of two of these three mental tasks showed the highest mean classification accuracies. It is expected that our results will be a useful reference to reduce the time needed for preliminary tests when discovering individual-specific mental task combinations.