Thin films of HfO2 were fabricated on a p-Si(001) substrate using double pulse excitation (DPE) pulsed laser deposition (PLD) with KrF excimer and Nd:YAG lasers, and using conventional Nd:YAG laser PLD under two typical oxygen pressures (7.3 × 10-2 and 7.3 × 10-1 Pa). At 400°C or higher temperatures, the films are crystalline; at less than 400°C, they are amorphous. At higher oxygen pressures, DPE-PLD was effective against droplets. Then the surface morphology and electrical insulation properties of thin films were improved. At lower pressure, DPE-PLD was ineffective.