Enhancing surface wetting is very critical for various applications of polymer films. Although existing modification methods (e.g., UV radiation and plasma treatments) can improve the wetting of polymer films by inserting hydrophilic groups, the resultant polymer surface is unstable and shows strong hydrophobic recovery in a short time (less than 1 day) due to the rearrangement of the polymer chains. Herein, we report a new approach to prepare stable wetting surface by cross-linking hydrophilic poly(acrylic acid) (PAA) molecules on poly(chloro-pxylylene) (PPXC) films via hyperthermal hydrogen induced crosslinking (HHIC) treatment. With the HHIC treatment, the polar functionalities of PAA (e.g., −COOH) can be preserved through selective cleavage of C−H bonds and subsequent cross-linking of resulting carbon radicals generated on PAA and PPXC chains. HHIC-treated PAA−PPXC film shows an excellent wetting stability, of which WCA and surface energy stay almost the same over 40 days. The improved wetting stability of PPXC film is attributed to the controllable HHIC reaction without undesirable side reaction (e.g., the scission of polymer chain backbone), which effectively restricts the rearrangement of PAA chains on the surface. Besides, the improved wetting stability by our approach results in reliable adhesion between silver ink and polymer films. Thus, fixing hydrophilic molecules on hydrophobic polymer surface by HHIC treatment could be an alternative approach to conventional surface treatments for preparation of stable wetting surface on polymer films.