The appearance of an S-shaped current-voltage curve and its impact on the performance of solution-processed small molecule p-DTS(FBTTh2)2:PC70BM bulk heterojunction solar cell devices were investigated. The power conversion efficiency of the devices showing S-curve characteristics was almost half of what was expected for this combination of materials, which was due to a low fill factor (FF) and 20% lower short circuit current density. A normal diode-like current-voltage curve was retrieved when the PCBM content of the active layer was increased, with power conversion efficiency reaching 6%. Analysis of the current-voltage characteristics of the S-curve solar cell devices showed that the effective voltage of the devices throughout the active layer was diminished due to an energy barrier. As a result, the charge collection efficiency was significantly affected. In addition, smaller external quantum efficiency (EQE) values in the absorption range of the small molecule donor in the S-curve devices suggested that charge generation was also affected. Recombination dynamics of both the normal and S-curve devices under steady-state conditions were quite similar. However, photovoltage decay results showed a distinguished pattern of recombination at open circuit conditions in the S-curve devices. This suggested different recombination rates at the cathode and anode electrodes, which is possibly due to the different composition of the donor-acceptor film near the contacts.