Tobacco-specific N-nitrosamines (TSNAs) and benzo[a]pyrene (B[a]P) in mainstream cigarette smoke (MSS) cause smoking-related diseases and environmental pollution. Porphyrins were added to cigarette filters to reduce B[a]P (porphyrins A-E) and TSNAs (porphyrin F) in MSS. The porphyrin-B[a]P and porphyrin F-TSNAs (N'-nitrosoanabasine (NAB), N'-nitrosoanatabine (NAT), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), and N-nitrosonornicotine (NNN)) interactions were investigated by fluorescence quenching and UV-visible spectroscopy. The correlation coefficients were 0.987-0.997 (B[a]P) and 0.994-0.999 (TSNAs), and the binding constants were (1.67-5.02) × 10(5) (B[a]P) and 3.42 × 10(3)-1.40 × 10(4) (TSNAs). Up to 36.72% of B[a]P and 46.67% of the TSNAs were eliminated from MSS, with greater reductions when more porphyrin was included in the filter. With the same mass of porphyrin in the filter, the reduction trend for B[a]P by porphyrins A-E was A > B > C > D > E. The reduction trend for TSNAs by porphyrin F was NNN > NAB > NNK > NAT. The porphyrin mode of action is possibly through strong π-π interactions.