The current–voltage (I–V) characteristics of the Al/NPB/p-Si contact shows rectifying behavior with a potential barrier formed at the contact interface. The barrier height and ideality factor values of 0.65 eV and 1.33 are measured at the forward bias of the diode. The barrier height of the Al/NPB/p-Si diode at room temperature is larger that (0.58 eV) of conventional Al/p-Si diode. It reveals the NPB organic film control the carrier transport of the diode at the contact interface. The temperature effect on the I–V measurement is also performed to reveal the junction characteristics. The ideality factor of the Al/NPB/p-Si contact increases with decreasing temperature. And the barrier height decreases with decreasing temperature. The effects are due to the existence of the interface states and the inhomogeneous of the barrier at the junction.