The welding titanium cathode roller has the obvious advantages of low cost, high efficiency, and no diameter restriction. Unfortunately, the longitudinal weld on the cathode roller adversely impacts the quality of the electrolytic copper foil due to the great difference between the microstructure of the weld zone and the base metal. Thus, it is crucial to reduce their difference by regulating the microstructure of the weld zone. In this study, a novel complex treatment of heat treatment and sandblasting is primarily developed for regulating the microstructure of the weld zone. The results show that the novel complex treatment has an efficient effect on regulating the microstructure of the weld zone and making the microstructure in the weld zone close to that of the base metal. During vacuum annealing, the microstructure of the weld zone is refined to some degree, and 650 °C annealing has the optimal effect, which can effectively reduce the ratio of α phase’s length to width and reduce the microstructure difference between the weld zone and the base metal. At the same time, with an increase in the annealing temperature, the tensile strength and yield strength decreased by about 10 MPa; the elongation after fracture increased by 20%; the average microhardness of the WZ and the HAZ decreased by about 10 HV0.10; and that of the BM decreased by about 3 HV0.10. The heat treatment after welding can effectively adjust the properties of the weld zone, reduce the hardness and strength, and improve the toughness. The subsequent sandblasting after annealing can further refine the grain size in the weld zone and make the microstructure in the weld zone close to that of the base metal. Sandblasting after annealing can further refine the grain in the weld zone and make the microstructure in the weld zone close to that of base metal. Meanwhile, an application test confirmed that the adverse impact of a longitudinal weld on the quality of electrolytic copper foil could be resolved by adopting this novel complex treatment. Therefore, this study provides valuable technical support for the “welding” manufacturing of the titanium sleeves of the cathode roller.