Gallium‐based liquid metal systems hold vast potential in materials science. However, maximizing their possibilities is hindered by gallium's native oxide and interfacial functionalization. In this study, small‐molecule ligands are adopted as surfactants to modify the surface of eutectic gallium indium (EGaIn) nanoparticles and suppress oxidation. Different p‐aniline derivatives are explored. Next, the reduction of chloroanric acid (HAuCl4) onto these p‐aniline ligand modified EGaIn nanoparticles is investigated to produce gold‐decorated EGaIn nanosystems. It is found that by altering the concentrations of HAuCl4 or the p‐aniline ligand, the formation of gold nanoparticles (AuNPs) on EGaIn can be manipulated. The reduction of interfacial oxidation and presence of AuNPs enhances electrical conductivity, plasmonic performance, wettability, stability, and photothermal performance of all the p‐aniline derivative modified EGaIn. Of these, EGaIn nanoparticles covered with the ligand of p‐aminobenzoic acid offer the most evenly distributed AuNPs decoration and perfect elimination of gallium oxides, resulting in the augmented electrical conductivity, and highest wettability suitable for patterning, enhanced aqueous stability, and favorable photothermal properties. The proof‐of‐concept application in photothermal therapy of cancer cells demonstrates significantly enhanced photothermal conversion performance along with good biocompatibility. Due to such unique characteristics, the developed gold‐decorated EGaIn nanodroplets are expected to offer significant potential in precise medicine.