An organic multifunctional device, which can function as an ambipolar field-effect transistor (FET) and a photovoltaic (PV) cell, has been demonstrated using a phase separated mixture of poly(3-hexylthiophene) and [6,6]-phenyl C-61-butyric acid methyl ester. The gold (Au) electrode used for hole injection in the FET mode (source) acts as the anode in PV cell mode, and the aluminum (Al) electrode for electron injection in the FET mode (drain) acts as the cathode in PV cell mode. The device exhibits clear PV phenomena under illumination at zero gate bias with a power conversion efficiency of 0.6% as well as the properties of an ambipolar FET when the gate bias is applied.