In three-dimensional (3D) packaging and assembly technology, Lead-free SnAgCu solder joints inevitably experience multiple reflows. The interfacial compounds of Sn3.0Ag0.5Cu (SAC305)/ Electroless Ni-P/Immersion Au (ENIG) solder bump after laser soldering and subsequent hot air reflows were observed by transmission electron microscopy (TEM), respectively. The initial laser soldering played a key role in interfacial compound evolution during the subsequent multiple reflows. After laser soldering, a thin P-rich layer and an ultrafine scallop-type (Ni, Cu) 3 Sn 4 layer formed at the interface of SAC305/ENIG. The valleys of ultrafine (Ni, Cu) 3 Sn 4 grains served as rapid channels for Ni diffusion, which contributed to the formation of dendritic η-(Cu, Ni) 6 Sn 5 + (Ni, Cu) 3 Sn 2 intermetallic compounds after the first hot air reflow. However, with the number of reflow times increasing, the η-(Cu, Ni) 6 Sn 5 totally transformed to noodle-like (Ni, Cu) 3 Sn 2 owing to their similarly hexagonal lattice structure and the limited Cu supply in solder.