In this work, we report an in situ surface X-ray diffraction study of the hydrogen electroinsertion in a two-monolayer equivalent palladium electrodeposit on Pt(111). The role of chloride in the deposition solution in favoring layer-by-layer film growth is evidenced. Three Pd layers are necessary to describe the deposit structure correctly, but the third-layer occupancy is quite low, equal to about 0.22. As a major result, resistance to hydriding of the two atomic Pd layers closest to the Pt interface is observed, which is linked to a strong effect of the Pt(111) substrate. As a consequence, we observe the lowering of the total hydride stoichiometry compared to bulk Pd. Our measurements also reveal good reversibility of the deposit structure, at least toward one hydrogen insertion−desorption cycle.