A　femtosecond　(fs)-laser-processed　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　processing.　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,　the　microlens　array　and　microfluidics　system　were　prepared　based　on　the　laser-induced　underwater　superpolymphobic　microstructures.　©　2019　American　Chemical　Society.