A plasma processing apparatus includes a process container configured to accommodate a target substrate and to be vacuum-exhausted. A first electrode and a second electrode are disposed opposite each other within the process container. A process gas supply unit is configured to supply a process gas into the process container. An RF power supply is configured to apply an RF power to the first electrode or second electrode to generate plasma of the process gas. A DC power supply is configured to apply a DC voltage to the first electrode or second electrode. A control section is configured to control the RF power supply and the DC power supply such that the DC power supply causes the DC voltage applied therefrom to reach a voltage set value, when or after the RF power supply starts applying the RF power.