Bimetallic AgAu Janus nanoparticles were prepared by galvanic exchange reactions of 1-hexanethiolate-passivated silver (AgC6) nanoparticles with gold(I)-mercaptopropanediol complex. The AgC6 nanoparticles were deposited onto a solid substrate surface by the Langmuir-Blodgett method such that the galvanic exchange reactions were limited to the top face of the nanoparticles that was in direct contact with the gold(I) complex solution. The resulting nanoparticles exhibited an asymmetrical distribution not only of the organic capping ligands on the nanoparticle surface but also of the metal elements in the nanoparticle cores, in contrast to the bulk-exchange counterparts where these distributions were homogeneous within the nanoparticles, as manifested in contact angle, UV-vis, XPS, and TEM measurements. More interestingly, despite a minimal loading of Au onto the Ag nanoparticles, the bimetallic AgAu nanoparticles exhibited enhanced electrocatalytic activity in oxygen reduction reactions, as compared to the monometal AgC6 nanoparticles. Additionally, the electrocatalytic performance of the Janus nanoparticles was markedly better than the bulk-exchange ones, suggesting that the segregated distribution of the polar ligands from the apolar ones might further facilitate charge transfer from Ag to Au in the nanoparticle cores, leading to additional improvement of the adsorption and reduction of oxygen.