For double-layer capacitors in alkaline electrolyte, the specific capacitance of the positive electrode is not equal to that of the negative one. Thus, capacitor performance cannot be optimal with a positive/negative electrode matching ratio of 1. In this study nanoporous glassy carbons (NPGCs) were employed as the electrodes of capacitors, and the influence of matching ratio between positive and negative electrode on capacitor performance was systematically investigated. In aqueous KOH, the specific capacitance of the positive electrode is lower than that of the negative electrode. The matching ratio at which a maximum capacitance is obtained is dependent on the values of the positive and negative electrode capacitance. At low current rate, the highest specific capacitance is achieved at a matching ratio slightly higher than 1. At high current rate, a capacitor has the highest specific capacitance with the lowest resistance at a matching ratio of 1.5. This indicates that an optimum matching relationship between positive and negative electrodes is attained.