Simultaneous monitoring of brain activity with near-infrared spectroscopy and electroencephalography allows spatiotemporal reconstruction of the hemodynamic response regarding the concentration changes in oxyhemoglobin and deoxyhemoglobin that are associated with recorded brain activity such as cognitive functions. However, the accuracy of state estimation during mental arithmetic tasks is often different depending on the length of the segment for sampling of NIRS and EEG signals. This study compared the results of a self-organizing map and ANOVA, which were both used to assess the accuracy of state estimation. We conducted an experiment with a mental arithmetic task performed by 10 participants. The lengths of the segment in each time frame for observation of NIRS and EEG signals were compared with the 30-s, 1-min, and 2-min segment lengths. The optimal segment lengths were different for NIRS and EEG signals in the case of classification of feature vectors into the states of performing a mental arithmetic task and being at rest.