A convenient ligand-free synthetic procedure has been developed to synthesize novel nickel(II) and copper(II) 2-aryloxazolo[5,4-b]-5,10,15,20-tetraarylporphyrins in 60–72% yields by a CuI-catalyzed intramolecular debrominative cyclization of 2-aroylamino-3-bromo-5,10,15,20-tetraarylporphyrins in dimethylsulfoxide containing potassium carbonate as a base. Subsequently, the copper(II) 2-(4-iodophenyl)oxazolo[5,4-b]-5,10,15,20-tetraphenylporphyrin underwent demetallation in the presence of concentrated sulfuric acid and afforded 2-(4-iodophenyl)oxazolo[5,4-b]-5,10,15,20-tetraphenylporphyrin in 75% yield which on zinc insertion using zinc(II) acetate in chloroform-methanol mixture provided zinc(II) 2-(4-iodophenyl)oxazolo[5,4-b]-5,10,15,20-tetraphenylporphyrin in 78% yield. The structures of newly constructed 2-aryloxazolo[5,4-b]-5,10,15,20-tetraarylporphyrins were assigned on the basis of spectral data and single crystal X-ray analysis. On photophysical investigation, these porphyrin analogues exhibit similar electronic properties as reported in the case of β-imidazole/thiazole-fused meso-tetraarylporphyrins.