Surface functionalization of metallic and semiconducting 2D transition metal dichalcogenides (TMDs) have mostly relied on physi- and chemi-sorption at defect sites, which can diminish the potential applications of the decorated 2D materials, as structural defects can have substantial drawbacks on the electronic and optoelectronic characteristics. Here, we demonstrate a spontaneous defect-free functionalization method consisting of attaching Au single atoms to monolayers of semiconducting MoS2(1H) via S-Au-Cl coordination complexes. This strategy offers an effective and controllable approach for tuning the Fermi level and excitation spectra of MoS2 via p-type doping and enhancing the thermal boundary conductance of monolayer MoS2, thus promoting heat dissipation. The coordination-based method offers an effective and damage-free route of functionalizing TMDs and can be applied to other metals and used in single-atom catalysis, quantum information devices, optoelectronics, and enhanced sensing.