A rapid fabrication method for conducting poly(vinylidene fluoride) by creating active centre using KrF excimer laser direct etching technique is demonstrated. Study shows that the etching point-defects and line-defects perform active centre function for facilely controlling conducting layer when laser irradiation decreases the laser threshold. The results of laser scanning confocal microscope(LSCM) and scanning electron microscope(SEM), indicate that the 2D net-like microstructures surround the defects are the precursor of conducting layer, which significantly affect the velocity of preparation. The effect of laser thermal cross-linking reaction and laser irradiation cross-linking reaction together contributes to the rapid formation of great conducting layer.