The changes that occur in the microstructure of crystalline and amorphous Cu-P-Sn-Ni filler metals during the heating process were studied by high-temperature microscopy, and the composition of solders at certain temperatures were analyzed by scanning electron microscopy and X-ray diffraction. The amorphous solder was observed to transform from amorphic to crystalline during the process of heating and distinct surface morphology changes were apparent, while the internal structure of the crystalline brazing filler metal was found to be relatively stable. During the heating process, the amorphous brazing filler metal formed a ϒ-Cu solid solution with a small amount of Cu3P compounds, Cu88Sn22 and (Cu, Ni)3P phase compounds, ultimately forming the Cu88Sn22 + Ni12P5 + (Cu, Ni)3P3 three-element eutectic structure.