In order to improve the plasticity of titanium alloy welded joints, relevant scholars currently focus primarily on studying the mechanism of action of alloying elements Mo and V, such as reducing the phase transition temperature of the welded seam and ensuring a certain amount of β phase residue in the welded seam. In addition to improving the stability and strengthening ability of titanium alloy welded joint, it can also maintain a certain degree of plasticity of the welded joint. However, the poor impact toughness is still the key problem that restricts its long-term stable service in the harsh environment. Our work designed and developed a new Ti–Al–Cr–Mo–Zr solid welding wire, with the synergistic effect of Al, Cr, Mo and Zr, the welded seam microstructure and grain can be refined while ensuring the enough stiffness of the welding wire and its flatness during wire feeding into the designated working area. It ensures good wetting and spreading flow performance of the liquid molten pool metal in the welding process, so better welded seam formation can be obtained. The relative contents of α′ martensite and β phase in the welded seam are 76.79% and 23.21%, respectively. The residual β phase is interspersed between the α′ martensite of the slats. The β phase provides a path for the plastic deformation of the welded joint, making it easier for dislocation slip to pass the β/α′ interface. At the same time, more dislocation slip channels and a small number of fine twins can be found in the interior of α′ martensite, which can ensure the strength while taking into account the toughness. After testing, it is found that the average tensile strength of welded joints is 901 MPa, which is close to 95% of the base metal (BM), the average post-fracture elongation of welded joints is 21%, and the impact toughness value at room temperature is distributed between 25 J and 33 J, which meets the requirements of the synergistic effect of welded joint strength and plastic toughness. It is suitable for long-term stable service of Ti64 titanium alloy welding structure under harsh working conditions.