A novel electro-codeposited film was homogeneously obtained on an indium tin oxide (ITO)-coated glass electrode by cathodic polarization of a solution of 2,9,16,23-tetracarboxyphthalocyaninatomagnesium(II) ( Mg II taPc ), N,N′-4-hydroxyphenyl-3,4,9,10-perylenetetra-carboxylic-diimide (4-hph-PTC) and ZnCl 2 as supporting electrolyte in N,N-dimethylformamide (DMF). The cyclic voltammogram for the codeposited film showed a reduction at −0.8 V vs SCE which was assigned to the reduction of Mg II taPc and one at −1.5 V vs SCE which was assigned to the reduction of 4-hph-PTC. A device based on the codeposited film was prepared by the formation of an aluminum electrode on the codeposited film. The device exhibited rectification and photoconduction. The results suggest that the codeposited film forms a number of p-n junction interfaces which are distributed on the ITO electrode.