Phase transformations and the melting range of the interlayer BNi-3 were investigated by differential scanning calorimetry, which showed three stages of crystallization during heating. There were three exothermic peaks that indicated crystallization in the solid state. The cobalt-based X-45 and FSX-414 superalloys were bonded with interlayer BNi-3 at a constant holding time of 10 min with bonding temperatures of 1010, 1050, 1100, and 1150 °C using a vacuum diffusion brazing process. Examination of microstructural changes in the base metals with light microscopy and scanning electron microscopy coupled with X-ray spectroscopy based on the energy distribution showed that increasing temperature caused a solidification mode, such that the bonding centerline at 1010 °C/10 min included a γ-solid solution, Ni3B, Ni6Si2B, and Ni3Si. The athermally solidified zone of the transient liquid phase (TLP)-bonded sample at 1050 °C/10 min involved a γ-solid solution, Ni3B, CrB, Ni6Si2B, and Ni3Si. Finally, isothermal solidification was completed within 10 min at 1150 °C. The diffusion-affected zones on both sides had three distinct zones: a coarse block precipitation zone, a fine and needle-like mixed-precipitation zone, and a needle-like precipitation zone. By increasing the bonding temperature, the diffusion-affected zone became wider and led to dissolution.