Treatment of 5,5'-dicarboxy-3,3',4,4'-tetraalkyl-2,2'-dipyrromethanes with trifluoroacetic acid and subsequent oxidation resulted in formation of meso-trifluoromethyl-substituted beta-octaalkylporphyrins. The structural characterizations and the spectroscopic measurements revealed their distorted conformations and red-shifted absorption bands depending on the steric bulkiness. Moreover, the corresponding Ni complexes were easily afforded and exhibited enhanced nonplanarities.