In the field of organic photovoltaic cells (OPVs), ternary planar heterojunction allows widening absorption range. Optimization of the energy levels at the organic interfaces is the first task to achieve in order to obtain OPVs with high efficiency. In ternary OPVs, carrier mobility, charge transfer and presence of energy transfer are determinant. Here, we compare the performances of different, binary (electron donor/fullerene) and ternary (electron donor/ambipolar material/fullerene) combinations of small organic molecules in planar heterojunction (PHJ) cells. We chose the different ED molecules in order to investigate the different possible band scheme alignments. The study shows that if the open circuit voltage (Voc) is limited by the energy levels of the outer layers, i.e. the difference between the lowest unoccupied molecular orbital (LUMO) of the electron acceptor and the highest occupied molecular orbital (HOMO) of the outer electron donor layer, the energy loss can be smaller than 0.2 eV. If efficient ternary OPVs need global energy offset higher than the exciton energy to separate the charges of the exciton, the distribution of this offset between Delta LUMO and Delta HOMO is not critical. The mobility value of the carriers in the intercalated layer is determinant in obtaining performance of OPVs. Overlap between the photoluminescence of E-D and the optical absorption of E-DA is primordial for good energy transfer. The highest OPV efficiency improvement is obtained with organic materials such as E-D and E-DA that have the same HOMO and similar hole mobility which give homogeneous thin layers.