Superhydrophobic poly (vinylidene fluoride) is rapidly prepared by KrF excimer laser irradiation at room temperature in ten seconds. The results show that the water contact angle on modified surfaces can be increased from 53° to approximately 170°. The morphologies and chemical construction of the modified layer before and after excimer laser irradiation are analyzed with atomic force micrograph(AFM) and X-ray photoelectron spectrometry(XPS). It is observed that a well 3D net-like microstructure is formed gradually on modified area, and the groups of C-CF2 and C-F become the subject of modified layer instead of CH2 and CF2. It is concluded that the effect of surface roughness increased and surface energy reduced together contribute to the observed superhydrophobic property of modified poly (vinylidene fluoride).