Optimizing the efficiency of heat dissipation across an interface is a great challenge with the continuously increasing integration of microelectronic devices. In this work, an effective method in tuning the heat conduction across the Al/graphene/SiO2 interface is reported. It was found that the interfacial thermal conductance of Al/irradiated graphene/SiO2 can be increased by a factor of 3, as compared with that of Al/pristine graphene/SiO2. The X-ray photoelectron spectroscopy (XPS) analysis indicates that ion irradiation may promote the formation of CO bonds on the irradiated graphene surface, which is beneficial to the enhancement of interfacial thermal conductance. The density functional theory (DFT) calculations reveal that in addition to the formed bonds between O atoms and Al atoms, the adsorption strength between Al and irradiated graphene is intensified, which plays a dominant role in enhancing the interfacial thermal conductance of Al/graphene/SiO2.