Hydrogen permeable electrodes can be utilized for electrolytic ammonia synthesis from dinitrogen, water, and renewable electricity under ambient conditions, providing a promising route toward sustainable ammonia. The understanding of the interactions of adsorbing N and permeating H at the catalytic interface is a critical step toward the optimization of this NH3 synthesis process. In this study, we conducted a unique in situ near ambient pressure X-ray photoelectron spectroscopy experiment to investigate the solid-gas interface of a Ni hydrogen permeable electrode under conditions relevant for ammonia synthesis. Here, we show that the formation of a Ni oxide surface layer blocks the chemisorption of gaseous dinitrogen. However, the Ni 2p and O 1s XPS spectra reveal that electrochemically driven permeating atomic hydrogen effectively reduces the Ni surface at ambient temperature, while H2 does not. Nitrogen gas chemisorbs on the generated metallic sites, followed by hydrogenation via permeating H, as adsorbed N and NH3 are found on the Ni surface. Our findings suggest that the first hydrogenation step to NH and the NH3 desorption might be limiting under the operating conditions. The study was then extended to Fe and Ru surfaces. The formation of surface oxide and nitride species on iron blocks the H permeation and prevents the reaction to advance; while on ruthenium, the stronger Ru-N bond might favor the recombination of permeating hydrogen to H2 over the hydrogenation of adsorbed nitrogen. This work provides insightful results to aid the rational design of efficient electrolytic NH3 synthesis processes based on but not limited to hydrogen permeable electrodes.