Under the trend of increasingly informationalized military operations and the increasing maneuverability of combat units, military commanders have put forward higher requirements for the accuracy and promptness of information on battlefield situation maps. Based on the sea battlefield, this paper studies the pros and cons of the color matching of military symbols on sea situation maps. Fifteen colors, where each Hue had five colors, were chosen using the Munsell Color System according to Chroma axis and the Value axis on a span of 2 and 4. By collecting and analyzing the P300 EEG data, reaction time data, and accuracy data of 20 subjects, a better color matching selection of military symbols on pure color (L = 85, a = −10, and b = −23) sea situation maps is put forward, and the conclusions are as follows: (1) the different colors all cause the P300 component in EEG experiment. Among them, the P300 amplitude that is caused by military symbols with lower Chroma is smaller and the latency is shorter, indicating that the user experience and efficiency of low Chroma color symbols will be better than those with high Chroma color symbols. (2) High Value color map military symbols cause higher P300 amplitude and longer latency. According to the results above, this paper puts forward three optimized colors, namely, blue (L = 39, a = 20, and b = −49), green (L = 80, a = −72, and b = 72), and red (L = 20, a = 41, and b = 28). Additionally, three map interfaces were designed to confirm the validity of these colors. By means of applying the NASA-TLX (Task Load Index) scale to evaluate the task load of the confirmation interfaces, it can be concluded that these three optimized colors are preferred by users who are skilled in GIS and interface design. Therefore, the research conclusion of this paper can provide important reference values for military map design, which is helpful in shortening the identification and judgment time during the use of situation maps and it can improve users’ operation performance.