Photoinduced intra- and intermolecular electron transfer (ET) in thin films of porphyrin-fullerene dyad (P-F) and perylenetetracarboxidiimide (PTCDI) was studied by means of photoelectrical and spectroscopic methods. Films consisting of smooth 100 mol% layers of P-F and PTCDI were prepared by the Langmuir-Schäfer (LS) technique and thermal evaporation, respectively. The time-resolved Maxwell displacement charge (TRMDC) and laser flash-photolysis methods were utilized to demonstrate photoinduced ET from P-F to PTCDI regardless of which chromophore is photoexcited. Finally, the information about the electron movement in the respective thin films was used to build a layered organic solar cell, whose internal quantum yield (Φ(I)) of collected charges was 13%.