A case of 4He enrichment in a spent palladium deuteride electrode is reported. The issue of helium isotope production related to the Fleischmann-Pons effect is still much in debate. In light of this important issue, two palladium samples, used in deuteride- and hydride-conducting molten salt electrolytes, and their corresponding blanks were analyzed for both 3He and 4He content. Four specimens from the deuteride sample, which has produced excess heat, showed significant 4He signals (enrichment) above the blank background level, while the hydride sample, used as a control with no excess heat measured, exhibited an opposite (depletion) effect. The 3He content remained unchanged, within the limits of the instrument's sensitivity. The amount of 4He detected was not commensurate with the excess heat according to known reaction mechanisms. The interpretation of the results was complicated by a substantial morphology difference among the samples. Because the level of helium content was small in magnitude, the possibility of atmospheric contamination cannot be dismissed completely.