The existence of interfacial carbides is a well-known phenomenon in Al/diamond composites, although quantitative analyses are not described so far. The control of the formation of interfacial carbides while processing Al(Si)/diamond composites is of vital interest as a degradation of thermophysical properties appears upon excessive formation. Analytical quantification was performed by GC-MS measurements of gaseous species released upon dissolving the matrix and interfacial reaction products in aqueous NaOH solutions and the CH4/N(2 )ratio of the evolving reaction gases can be used for quantification. Although the formation of interfacial carbides is significantly suppressed by adding Si to Al, also a decline in composite thermal conductivity is observed in particular with increasing contact time between the liquid metal and the diamond particles during gas pressure infiltration. Furthermore, surface termination of diamond particles positively affects composite thermal conductivity as oxygenated diamond surfaces will result in an increase in composite thermal conductivity compared to hydrogenated ones. In order to understand the mechanisms responsible for all impacts on the thermal conductivity and thermal conductance behaviour, the metal/diamond interface was electrochemical etched and characterized by SEM. Selected specimens were also cut by an ultrashort pulsed laser system to characterize interfacial layers at the virgin cross section in the reactive system Al/diamond.