摘要： A femtosecond (fs) laser-ablated surface that repels liquid polymer in water is reported in this paper. We define this phenomenon as the “superpolymphobicity”. Three-level microstructures (including microgrooves, micromountains/microholes between the microgrooves, and nanoripples on the whole surface) were directly created on the stainless steel surface via fs laser ablation. A liquid polydimethylsiloxane (PDMS) droplet on the textured surface had the contact angle of 156 ± 3° and contact angle hysteresis less than 4° in water, indicating excellent underwater superpolymphobicity of the fs laser-induced hierarchical microstructures. The contact between the resultant superhydrophilic hierarchical microstructures and the submerged liquid PDMS droplet is verified at the underwater Cassie state. The underwater superpolymphobicity enables to design the shape of cured PDMS and selectively avoid the adhesion at the PDMS/substrate interface, different from the previously reported superwettabilities. As the examples, microlens array and microfluidics system were prepared based on the laser-induced underwater superpolymphobic microstructures.