Gas tungsten arc welding with a pure Cu filler wire was carried out to join the TC4 titanium alloy and 304 stainless steel. Filling pure Cu filler wire assisted with regulating welding current could effectively restrain the concentrated generation of Ti-Fe brittle intermetallic compounds. Three joining modes exist in the fusion welding titanium alloy and stainless steel. In the partial fusion welding mode, the TiCu phase decreased and the fine granular τ 2 phase formed in the Ti/Cu interfacial zone, simultaneously, the molten zone consisted of a Cu solid solution and α-(Fe, Cr) phase formed at the Cu/Fe interface, resulting in mechanical interlocking effect and consequent high tensile strength of 363 MPa. Increasing the welding current would lead to the alloying of Ti x Cu y phases, and then enhance the Ti/Cu interface.