Based on the predesigned self-selective complexation, metallo-supramolecular P3HT-b-PEO diblock copolymers with varying block ratios were synthesized, and their oriented polymer films generated during solvent evaporation in a 9 T magnetic field were investigated. An anisotropic, ordered layer structure was achieved using [P3HT20 -Zn-PEO107 ] and carefully characterized by polarized optical microscopy (POM), AFM, polarized UV/Vis spectroscopy, and GI-SAXS/WAXS. The PEO-removed [P3HT20 -Zn-PEO107 ] film was obtained after decomplexation with TEA-EDTA under mild conditions, and the selective removal of PEO domains was evidenced by UV/Vis and ATR-FTIR spectroscopy. Anisotropic photoconductivity of the magnetically aligned film was evaluated by flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements. The results indicated that the presence of insulating crystalline PEO segments diminished the photoconductivity along the P3HT backbone direction.