Electrical breakdown in alkali metal thermal-to-electric converters (AMTECs) limits the number of solid electrolytes that could be connected in series and, hence, the output voltage. Experiments are conducted to measure the DC electrical breakdown voltage in cesium vapor between two planar molybdenum electrodes, 1.6 cm in diameter, separated by a 0.5 mm gap, and relate the results to potential electrical breakdown on the cathode side of AMTECs. Two sets of experiments are conducted. In the first set, in which the electrodes are kept at 560 and 650 K and the cesium pressure varied from 0.71 to 29 Pa, when the cooler electrode is positively biased, breakdown occurs at ∼500 V. When the cooler electrode is negatively biased, breakdown occurs at 700 V. In the second set of experiments, in which the electrodes are held at 625 and 1100 K and the cesium pressure varied from 1.7 to 235 Pa, when the cooler electrode is positively biased, the breakdown voltage is <4 V but in excess of 400 V when the cooler electrode is negatively biased. Because the first ionization potential (3.89 V) and the ionization rate constant of cesium are lower and higher, respectively, than for sodium (5.14 V) and potassium (4.34 V) vapors, the DC electrical breakdown voltage in AMTECs with either a potassium or a sodium working fluid is expected to be higher than measured in this work for cesium vapor. In such converters, the wall should be negatively biased relative to the highest voltage cathode in order to avoid electrical breakdown up to 400 V, or even higher.