A divergent one-pot domino strategy for the synthesis of nickel(II) and copper(II) β-thiophene-fused 5,10,15,20-tetraarylporphyrins was developed through a thiol-Michael addition of thioglycolic/thiolactic acid to the corresponding 2-iminoporphyrins, formed in situ after the reaction of nickel(II) and copper(II) 2-formyl-5,10,15,20-tetraarylporphyrins with sterically hindered tert-butylamine in 1,2-dichloroethane at 80 °C. Interestingly, the reaction of 2-formylporphyrins with comparatively less sterically hindered primary amines and thioglycolic acid afforded a mixture of β-substituted porphyrinic thiazolidinones and β-thiophene-fused porphyrins. A similar one-pot thiol-Michael protocol was applied to construct a novel free-base thieno[2,3-b]-meso-tetrakis(4-methoxyphenyl)porphyrin, which underwent zinc insertion by using zinc acetate in a CHCl3-MeOH mixture and afforded zinc(II) β-thiophene-fused meso-tetrakis(4-methoxyphenyl)porphyrin in an appreciable isolated yield. On photophysical evaluation, these new porphyrins displayed a modest bathochromically shifted electronic absorption in contrast to meso-tetraarylporphyrin building blocks.