Reactive　multilayer　thin　films　are　well-defined　heterogeneous　nanostructured　energetic　materials　which　can　release　chemical　energy　through　a　self-sustainable　reaction.　They　have　attracted　intense　interests　due　to　potential　applications　in　diverse　fields　such　as　joining,　igniters,　and　high　energy　density　power　sources.　In　this　paper,　Ti/Ni,　Ti/Al　and　Ni/Al　multilayer　films　were　prepared　by　magnetron　sputtering.　The　reaction　kinetics,　microstructure　and　phase　variation　of　these　free-standing　films　are　comparatively　investigated.　During　slow　heat　reaction,　the　reaction　products　of　reactive　multilayer　Ti/Ni　nanofoils　change　from　B2-TiNi　austenite　phase　into　TiNi3,　illustrating　an　evolution　of　the　phase　transformation　during　reaction.　These　intermediate　phases　are　also　identified　by　slow　heating　and　quenching.　The　fast　speed　imaging　exhibits　that　the　front　speed　is　0.47m/s,　0.8m/s　and　3m/s　respectively　for　as-deposited　Ti/Ni,　Ti/Al,　and　Ni/Al　films.　Differential　thermal　analysis　yields　that　the　corresponding　releasing　heat　is　551.44　J/g,　434.18　J/g,　and　562.5　J/g　for　these　three　composites.　The　theoretical　minimum　multilayer　thickness　for　melting　a　tin　solder　layer　has　been　calculated　on　the　base　of　these　characterizations,　which　proved　the　application　potential　of　joining　using　the　as-deposited　film.