Spin-coated organic blends of the five-ring PPV-type oligomer 2,5-di-n-octyloxy-1,4-bis((4′,4″-bisstyryl)styrylbenzene) (Ooct-OPV5) and polystyrene (PS) have been investigated in order to retrieve relevant parameters for the simulation of Schottky diodes of the type ITO/Ooct-OPV5:PS (1:1)/Al. A value of 0.53eV for the Schottky-barrier formed at the Al/oligomer was determined by temperature-dependent IV-measurements. From the CV-characteristics of the same diode structures, an upper limit of 3.3×10 15 cm −3 for the (p-type) doping concentration could be obtained. Thin film transistors have been fabricated to derive a value of 9×10 −5 cm 2 /Vs for the mobility of the holes in a Ooct-OPV5:PS layer. The experimentally-determined parameters were used as input for numerical simulations. A good correspondence was found between the simulated and the experimental dark IV-curves of the ITO/Ooct-OPV5:PS (1:1)/Al device structure. For the illuminated IV-curves, a large difference between the experimental and simulated short-circuit photocurrent was observed due to incomplete dissociation of excitons.