A charge-transfer complex based on axially CN-substituted iron tetrabenzoporphyrin has been fabricated. X-ray structure analysis reveals that the differences in the distances and angles around the meso positions between tetrabenzoporphyrin and phthalocyanine are substantial between the porphin and porphyrazine frameworks. Electrical transport measurements reveal semiconducting behavior with higher activation energy due to the reduction in pi-pi it overlapping, compared to an isostructural phthalocyanine complex.