A convenient approach for the synthesis of β-substituted α,β-unsaturated carbonyl porphyrin compounds via base-catalyzed aldol reaction was developed. By this method, a series of β-substituted α,β-unsaturated carbonyl porphyrin compounds were constructed using β-porphyrin formaldehyde and ketones with moderate to excellent yields under mild reaction conditions, especially solvent-free, and good functional group tolerance. Furthermore, this process was successfully applied to the reactions of different metal porphyrin which have been reported to have poor reaction effects with good yields.