Porphyrins (pors) are macrocyclic compounds consisting of four pyrrole units and characterized by strong absorption bands in the visible region, redox behavior, and unique metal coordination ability due to their large p-conjugated system and N atom-inward structure. This chapter focuses on the synthesis and structural characterization of multiple-decker tetrapyrrolic compounds. Benzoporphyrin is a genuine counterpart of phthalocyanine from the molecular framework point of view. All types of benzoporphyrins were prepared in a manner similar to the literature. By a one-pot reaction with bicyclo[2.2.2]octadiene-fused precursors, various multiple-decker complexes with p-extended pors and bisporphyrins can be obtained. Multidecker metal pors exhibit several metastable oxidation states and characteristic absorption in the visible region. Investigation of their magnetic and conducting behavior in a partially oxidized and photoexcitation state can lead to the development of new materials.