HfO₂ and Y₂O₃ doped HfO₂ thin films were deposited using PLD on YSZ (001) substrate. The film composition and effect of Y₂O₃ on HfO₂ thin films were investigated using the X-ray photoelectron spectroscopy (XPS) techniques. From the XPS analysis it was observed that due to Y₂O₃ doping the oxygen vacancy decreases in Y10 thin film as compare to Y0 thin film and further increases for Y20 thin film. A mixed phase formation of Hf-O-Y was observed in doped HfO₂ thin film as Y₂O₃ doping increased from 10% in Y10 thin film to 20% in Y20 thin film.