The reaction of ((tetraphenylporphyrinyl)methyl)triphenylphosphonium chloride and benzaldehydes (CHO-C6H4-R; R = H, NO2, NMe2, OMe, Me, CHO) yields the styryl porphyrin derivatives. These new styryl-substituted porphyrins have been studied using electrochemistry, electronic absorbance, and resonance Raman spectroelectrochemical techniques. The substituents on the styryl group have a modest perturbation on the electronic spectrum of the porphyrin core. The resonance Raman data suggest that a charge-transfer interaction is observed between the porphyrin core and the NO2 group for the 4-NO2 compound.