AbstractPlumbene, with a structure similar to graphene, is expected to possess a strong spin–orbit coupling and thus enhances its superconducting critical temperature (Tc). In this work, a buckled plumbene‐Au Kagome superstructure grown by depositing Au on Pb(111) is investigated. The superconducting gap monitored by temperature‐dependent scanning tunneling microscopy/spectroscopy shows that the buckled plumbene‐Au Kagome superstructure not only has an enhancedTcwith respect to that of a monolayer Pb but also possesses a higher value than what owned by a bulk Pb substrate. By combining angle‐resolved photoemission spectroscopy with density functional theory, the monolayer Au‐intercalated low‐buckled plumbene sandwiched between the top Au Kagome layer and the bottom Pb(111) substrate is confirmed and the electron–phonon coupling‐enhanced superconductivity is revealed. This work demonstrates that a buckled plumbene‐Au Kagome superstructure can enhance superconductingTcand Rashba effect, effectively triggering the novel properties of a plumbene.