meso-Tetra (2′- and 3′-thienyl)porphyrins and their Zn(II)-complexes were examined by steady-state fluorescence measurements. These molecules exhibit significant bathochromic shift in their emission bands with decreased quantum yields relative to their correspondingmeso-tetraphenylporphyrin derivatives. The crystal structure of 5,10,15,20-tetrakis(3′-thienyl)porphinato zinc(II) shows planar and nonplanar stereochemical features of the macrocycle. One of the macrocycle shows nearly planar while the other exhibited predominantly saddle-shaped geometry. The extent of displacement of the Β-pyrrole carbons in the nonplanar (saddle) conformation is as high as ± 0·422 Å.