The influence of the thiophene ring on the ground and excited state properties of the porphyrin ring is investigated, when substituted at the meso-position. A series of mono-, di-, tri-, and tetra-meso-thien-2-yl porphyrins are studied and discussed with respect to the reference compounds zinc(II)-5,10,15,20-tetra(thien-2′-yl)porphyrin (1a) and zinc(II)-5,10,15,20-tetraphenylporphyrin (ZnTPP). The extended conjugated system zinc(II)-5-(5′-(5′′-ethynyl-2′′-thiophenecarboxaldehyde)thien-2′-yl)-10,15,20-triphenylporphyrin (4d) is also studied and shows enhanced charge transfer character due to the presence of the terminal aldehyde accepting group. A detailed analysis of ground and excited state UV−vis absorption, steady-state and time-resolved fluorescence, laser flash photolysis, and electrochemical data all point toward substantial electronic communication between the central Zn(II) porphyrin ring and the meso-thien-2-yl substituents, which is evident from excited state charge transfer character.