Inserting modification layers at the diamond/Al interface is an effective technique in improving the interfacial thermal conductance (ITC) of the composite. However, few study reports the effect of interfacial structure on the thermal conductivity (TC) of diamond/Al composites at room temperature. Herein, the scattering-mediated acoustic mismatch model, suitable for evaluating the ITC at room temperature, is utilized to predict the TC performance of the diamond/Al composite. According to the practical microstructure of the composites, the reaction products at diamond/Al interface on the TC performance are concerned. Results indicate that the TC of the diamond/Al composite is dominantly affected by the thickness, the Debye temperature and the TC of the interfacial phase, meeting with multiple documented results. This work provides a method to assess the interfacial structure on the TC performance of metal matrix composite at room temperature.