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. The first electrode includes an outer portion and an inner portion both facing the second electrode such that the outer portion surrounds the inner portion. An RF power supply is configured to apply an RF power to the outer portion of the first electrode. A DC power supply is configured to apply a DC voltage to the inner portion of the first electrode. A process gas supply unit is configured to supply a process gas into the process container, wherein plasma of the process gas is generated between the first electrode and the second electrode.