Reaction of various α-unsubstituted pyrrole derivatives with trimethyl(porphyrinylmethyl)-ammonium iodides (generated in situ from the corresponding meso-dimethylaminomethylporphyrins and iodomethane) afforded a number of symmetrical and unsymmetrical porphyrinylmethylpyrrole adducts, including dimers linked by one and two pyrrolylmethylene units. The NMR spectra of the monopyrrole-linked dimers indicate a preference for a face-to-face conformation.