The electronic structures at the interfaces of iron phthalocyanine (FePc)/TiO2(110), FePc/C60 and FePc:C60 blends are studied in situ by synchrotron radiation-based ultraviolet photoelectron spectroscopy (SRUPS). It is found that the interaction between organic molecules and the surface of reduced rutile TiO2(110) is stronger than that of the stoichiometric TiO2(110) interface. The energy level alignments at the FePc/C60 interface and FePc:C60 blends are drawn based on the evolutions of the interfacial electronic structures. From the SRUPS spectra, the band bending energies are found to be 0.45 eV in the C60 layer and 0.1 eV in the FePc layer at the FePc/C60 interface. The interface dipole energy is 0.2 eV at the FePc/C60 interface. The offsets between the HOMO of FePc and LUMO of C60 are 0.85 eV at FePc/C60 and 1.04 eV at FePc:C60 blends, which indicates that the blend films can improve the efficiency of the relevant optical-electric devices.