Hybrid poly(3-hexylthiophene)/ZnO devices are investigated as rectifying heterojunctions for microelectronics applications. A low-temperature atomic layer deposition of ZnO on top of poly(3-hexylthiophene) allows the fabrication of diodes featuring a rectification ratio of nearly 105 at ±4 V and a current density of 104 A/cm2. Electrical characteristics are discussed taking into account the chemical structure of the stack and the energy band diagram.