Polymer barrier materials have been increasingly used in many applications such as metal anti-corrosion, electronic packaging, and cultural relic protection, but they have poor resistance to water vapor compared to inorganic barrier materials. Herein, we demonstrate the first application of hyperthermal hydrogen induced cross-linking (HHIC) technology to improve dramatically the water vapor barrier properties of Poly(chloro-p-xylylene) (PPXC) films by building a dense and intact surface cross-linking layer. With the HHIC treatment, the dense cross-linked layer is formed on the surface of the PPXC film, which serves as a dense barrier layer to water vapor diffusion. The water vapor transmission rate of PPXC film sharply decreases from 8.4×10 -16 to 2.1×10 -16 g·cm/cm 2 ·s·Pa by 75% after 5 min HHIC treatment. Due to the advantage of selective cleavage of C-H bonds by HHIC treatment, the desired chloride groups and original physical properties (e.g. mechanical strength and light transmittance) were well preserved.