Free base 5,10,15,20-tetrakis(4-n-octylphenyl) porphyrin (H{sub 2}TOPP) belongs to a class of self-organizing porphyrins. Since its LUMO lies above the conduction band of titanium dioxide (TiO{sub 2}) and its visible light absorption is very strong, sensitization of TiO{sub 2} with H{sub 2}TOPP thin films is possible. After spin-coating this porphyrin onto n-type TiO{sub 2}, the Fermi-level of H{sub 2}TOPP is measured, from which it is established that it behaves as intrinsic semiconductor, i.e., donor and acceptor densities, if present, compensate each other. Thin films of zinc 5,10,15,20-tetrakis(4-carboxyphenyl) porphyrin (ZnTCPP) are also investigated and show profound p-type character. Moreover, the LUMO of ZnTCPP is located about 0.4 eV above that of H{sub 2}TOPP making an organic based heterostructure p-i-n solar cell possible. In this cell, H{sub 2}TOPP is sandwiched between n-type TiO{sub 2} and p-type ZnTCPP. The LUMO positions of these porphyrins is such that unidirectional energy transfer from ZnTCPP to H{sub 2}TOPP occurs. By carefully comparing the photocurrent action spectra with the absorption spectra, it could be established that a built-in field in the p-i-n structure is beneficial for solar-energy conversion.