To facilitate analysis of nanoscale heat transfer in nanoparticle systems the thermal properties of ligand layers must be understood. To this end, we use an optical pump-probe technique to study the thermal transport across ligands on gold nanorods and into the solvent. We find that varying properties of the ligand can have large impacts on the thermal decay of a nanorod after exposure to a laser pulse. By raising the concentration of free CTAB from 1 mM and 10 mM in solutions, the CTAB layer’s effective thermal interface conductance increases three fold. The transition occurs near the CTAB critical micelle concentration. Similar results are found for other ligand layers.