In the brazing joint between titanium alloy and stainless steel, a lot of Fe-Ti intermetallic compounds (IMCs) can be easily formed to make joints crack. A lap resistance brazing process with metal powder layers on both sides of the filler metal was used to solve this problem. The microstructure and metallurgical behavior of joints was studied through comparative experiments. The result showed that Nb, V and Cr powders and the solder reacted with the base material to form a new phase, which replaced the Ti-Fe brittle phase in the joint. At the same time, metal powder clusters hindered the diffusion of Ti and Fe elements and improved the distribution of new phases. The established atomic reaction model revealed the metallurgical behavior and formation mechanism of the joints. Therefore, the intervening position of the metal powder layer and the multi-reaction zone structure are the main reasons the shear strength of joints is improved.