The mesoporphyrin dimethyl ester nickel complex has been formylated via the Vilsmeier method. The four possible mono meso-formyl derivatives were isolated and characterized. Wadsworth−Emmons coupling with the anion of (diethylphosphono)acetonitrile converted these aldehydes into the four novel meso acrylonitriles. Brief treatment of these acrylonitrile systems in hot trichloroacetic acid resulted in the formation of four achiral porphyrin derivatives with unprecedented nickel complexes of quino-fused porphyrins. Subsequent removal of the nickel gave four quino-porphyrin free bases: quino[4,4a,5,6-efg]-annulated 7-demethyl-8-deethylmesoporphyrin dimethyl ester 6a, 2Ј-(methoxycarbonyl)quino-[4,4a,5,6-jkl]-annulated 12-demethyl-13-de[2Ј-(methoxycarbonyl)ethyl]mesoporphyrin dimethyl ester 6b, 2Ј-(methoxycarbonyl)quino [4,4a,5,6-qrs]-annulated 18-demethyl-17-de(2Ј-methoxycarbonylethyl)mesoporphyrin dimethyl ester 6c and quino [4,5,6,7-abt]-annulated 2-demethyl-3-deethylmesoporphyrin dimethyl ester 6d. The structures of these systems were unambiguously determined via mass spectroscopy and a plethora of NMR techniques. In the same way, etioporphyrin and octaethylporphyrin were converted into the corresponding peri-condensed quinoporphyrins as products, which shows that the formation of novel peri-