In this work, the surfaces that repel liquid polydimethylsiloxane (PDMS) droplets in water were created by femtosecond laser treatment. We define this superwetting phenomenon as underwater "superpolymphobicity". The resultant underwater superpolymphobic silicon surface shows a contact angle of 159 ± 1° and a sliding angle of 1.5 ± 0.5° to liquid PDMS droplets in water. This underwater superpolymphobicity can be achieved on a wide range of hydrophilic materials, including semiconductors, glass, and metals. The adhesion between the liquid polymer and a solid substrate is effectively prevented by the underwater superpolymphobic microstructures. The underwater superpolymphobicity will have a great significance in designing the adhesion between the polymer and a solid substrate, controlling the shape of the cured polymer materials, as well as nearly all the applications based on the polymer materials.