A novel high thermal conductivity joining between diamond heat sink and light emitting diode (LED) chip was investigated. AlNi nano/micro-multilayers were fabricated and used to test the bonding of copper and diamond by self-propagation. The thermal analysis results and micro structure observation show that the bilayer (one alternative sputtering period of aluminium and nickel layers) of the mulilayer will influence the heat release of propagation reaction, and hence help to control the bonding process with steady. The influence of the vanadium addition and the magneto-conductivity of nickel element on the structures of the multilyers were also discussed, which has relation with the bilayer either. The quality of the diamond-copper joint by nano-multilayer bonding is better than that of the silver glue bonding in shearing strength and thermal conductivity