In this work, MoNx films deposited by reactive sputtering are investigated as cap layers on HfO2 gate dielectrics. A phase transition from body-centered-cubic Mo phase to face-centered-cubic (FCC) γ − Mo2N phase is found with increasing nitrogen content and causes a morphology change. It is found that the crystallinity and grain size decrease when MoNx films are subjected to phase transition. The Mo 3d core levels shift toward higher binding energy due to increments of nitrogen in the MoNx films. The resistivity and work function are also seen to have positive dependence on the nitrogen content. The work functions extracted from the capacitance vs. voltage curves are 4.58 eV for Mo films and 5.10 eV–5.23 eV for MoNx films on HfO2 gate dielectrics, respectively.