Hydrophilic surface modification of poly(tetrafluoroethylene) (PTFE) has been carried out by coating with a thin layer of fluoroalkyl-terminated poly(ethylene gylcol) (PEG). The coating layer adheres by hydrophobic interactions and is stable, in accord with the sol-gel behavior of the bulk polymer. Stable hydrogel arrays have been prepared by e.g., solvent-assisted micromolding on a perfluorosilanized substrate (see Figure).