Plumbene, 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 enhanced Tc with 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 superconducting Tc and Rashba effect, effectively triggering the novel properties of a plumbene.