Silylation of peripherally lithiated porphyrins with silyl electrophiles has realized the first synthesis of a series of directly silyl-substituted porphyrins. The meso-silyl group underwent facile protodesilylation, whereas the -silyl group was entirely compatible with standard work-up and purification on silica gel. The meso-silyl group caused larger substituent effects to the porphyrin compared with the -silyl group. Silylation of -lithiated porphyrins with 1,2-dichlorodisilane furnished -to- disilane-bridged porphyrin dimers. A doubly -to- disilane-bridged Ni-II-porphyrin dimer was also synthesized from a ,-dilithiated Ni-II-porphyrin and characterized by X-ray crystallographic analysis to take a steplike structure favorable for interporphyrinic interaction. Denickelation of -silylporphyrins was achieved upon treatment with a 4-tolylmagnesium bromide to yield the corresponding freebase porphyrins.