Ti6Al4V (TC4) alloy has been widely applied in the military, industrial, chemical, and medical fields due to their excellent thermal stability, corrosion resistance, and biocompatibility. However, titanium alloys are notorious for their poor tribological properties, such as their high friction coefficients and low surface bearing capacities. To tackle this problem, combination of laser surface texturing (LST) and double glow plasma chromizing was conducted to improve the wear resistance of TC4. LST was first conducted to produce uniform dimples with a diameter of 300 μm and gradient density of 11 % on the Ti6Al4V substrate. A chromizing coating (Cr-coating) was subsequently deposited on the surfaces of the textured and raw Ti6Al4V alloy by double glow plasma surface alloying (DGPSA). A continuous and compact Cr-coating with a thickness of about 55 μm was formed on TC4 after being maintained at a temperature of 850 °C, and the coating was mainly composed of a solid solution and intermetallic compounds of Cr2Ti phases. The surface hardness after alloying was two times higher than that of the TC4 substrate. Comparative assessments on the wear resistance of the Cr-coatings with and without LST treatment and the TC4 alloy were carried out using a ball-on-disk wear tester. The results showed that the mass loss and specific wear rate of the duplex-treated sample were 1.54 mg and 7.14 × 10−4 mm3·N−1·m−1. The mass loss and specific wear rate of the TC4 were 4.32 mg and 1.62 × 10−3 mm3·N−1·m−1. The wear rates of the four tested samples were in the following order: the duplex-treated TC4 < chromized TC4 < textured TC4 < polished TC4. The coating obtained by LST-double glow plasma chromizing duplex treatment exhibited an outstanding durability and the best mechanical performance. Thus, this approach can be used for the protection of Ti6Al4V surfaces in engineering components and medical instruments.