Titanium/steel clad material with excellent mechanical properties and corrosion resistance has important application in the oil, gas and ocean equipment. Due to the metallurgical incompatibility of titanium and steel, the mechanical properties of weld joint would completely lose when the brittle intermetallic phase existed in the fusion welding process. Therefore, the gas tungsten arced welding (TIG) + metal inert-gas welding (MIG) + metal active-gas welding (MAG) with pure vanadium and pure copper composite filler metals for welding connection experiment in this study was carried out on Ø610mm×(14+2)mm TA1/X65 titanium/steel clad pipe fitting (titanium cladding with thickness 2 mm, X65 pipeline steel with thickness 14 mm). The microstructure, interface element distribution, main phase, microhardness distribution on cross section and mechanical properties of butt welds were researched by using OM, XRD, EDS element mapping, microhardness and tensile tests. The result showed that the use of pure vanadium and pure copper composite filler metals for welding connection could effectively avoid the production of intermetallic compounds in the process of titanium/steel composite pipe fusion welding. The deposited metal of titanium, vanadium, copper and steel had obvious zoning, the inter-diffusion melting phenomenon was not severe, which is by using solid solution phases to transit zonings of deposited metal. The microstructure of titanium and vanadium transition interface were composed of titanium-based solid solution, the microstructure of vanadium and copper transition interface was composed of vanadium-based solid solution, and the microstructure of copper and steel transition interface were composed of copper-based solid solution. The transition interface had no porosity, crack and other defects. The tensile strength of the weld was 546MPa, which is mainly contributed by the carbon steel layer. With pure vanadium and pure copper as transition filler metal for the welding connection TA1/X65 clad pipe was successfully realized by TIG+MIG+MAG welding method, and the strength index reached the desired effect.