Ti6Al4V alloy with excellent mechanical, physical, and chemical properties is now widely used in marine, aerospace, and biomedicine industry. Endowing Ti6Al4V alloy with better surface performances is of great significance and value. Herein, a convenient and commercial nanosecond laser etching method is utilized to fabricate a novel multiscale micro/nano porous structure based on Ti6Al4V alloy. Following the modification of the fluoroalkylsilane and the infusion of silicon oil, the slippery liquid‐infused porous surface (SLIPS) is successfully obtained. The wettability is studied in detail and indicates the SLIPS possesses excellent sliding property and hydrophobicity. The volume of the droplet and sample temperature are confirmed to have some significant impact on the sliding angles. Accordingly, a variety of liquids are able to slide down the tilted SLIPS (15.9°), indicating that the as‐prepared SLIPS demonstrates extraordinary liquid‐repellent ability. In addition, the multiscale micro‐/nanoporous structures can lock the silicon oil firmly and form a stable oil film on the surface, so the SLIPS also shows desirable self‐cleaning, self‐healing, and stability properties. Based on the study, it is promising that the SLIPS as‐prepared may expand the practical application of conventional Ti6Al4V alloy materials.