The ruffle of the porphyrin increases with the number of meso substituents. (Octaethylporphyrin)nickel(II) undergoes nucleophilic substitution reactions upon treatment with alkylating reagents such as butyllithium, hydrolysis with water, and oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone [DDQ; Eq. (a)]. Alkylation can be achieved at all four meso positions, and access is provided to new nonplanar porphyrins and asymmetrically substituted systems.