The work aims to improve the hydrophilia of selective laser melted (SLMed) Ti6Al4V alloy. The surface of SLMed Ti6Al4V alloy was modified by controlling laser energy density and pulse number of 248 nm KrF excimer laser. Scanning electron microscopy (SEM) and laser scanning confocal microscope (LSCM) were used to characterize the surface morphology and roughness before and after laser irradiation, energy dispersive X-ray spectrum (EDS) and X-ray diffraction (XRD) were employed to analyze the surface components of specimens after laser irradiation and contact angle measuring system was applied to characterize the wettability of specimen surface. When the excimer laser energy density was controlled from 0 to 531 mJ/cm2 with the pulse numbers of 50, the contact angles of specimens decreased from (116±4)° to (7.5±0.4)°. Meanwhile, through surface observation, the surface of Ti6Al4V after excimer laser irradiation became smoother and the surface roughness was improved, decreasing from (40.3±3.7) μm to (8.3±1.7) μm. Moreover, an increase content of oxygen element from 0wt% to 33.54wt% was detected and TiO generated due to the reaction between Ti6Al4V specimens and oxygen. Based on Cassie-Baxter model and 3D surface morphology of the specimens, the surface of Ti6Al4V alloy after laser irradiation became smoother, which increased the percentage of solids in the solid-liquid-gas composite interface, leading to the specimens becoming more hydrophobic. Timeliness test showed that the surface contact angle of the specimens was stable within 48 hours. Therefore, the surface roughness of SLMed Ti6Al4V alloy can be decreased effectively and rapidly and the surface hydrophilia can be improved and controlled by changing energy density of excimer laser irradiation.