In this work, supramolecular fixation of three amines, including aniline, ethylenediamine, and diethylamine, using cobalt tetraphenylporphyrin (CoTPP) for SO2 removal was studied using UV-Vis and fluorescence measurements. The UV-Vis spectra showed that increasing amines concentrations resulted in bathochromic shift for CoTPP Soret absorption band (B band). Once SO2 was introduced, it competed with CoTPP for aniline, ethylenediamine, and diethylamine, which eventually led to the release of CoTPP and the change of solution colour/absorption band. After that, the CoTPP was regenerated and got back to the first state. The fluorescence spectra offered that CoTPP interacted with aniline, ethylenediamine, and diethylamine to form 1:1 molecular adducts. The interactions of CoTPP with aniline, ethylenediamine, and diethylamine were entropy-driven. The interaction of CoTPP with aniline and diethylamine was endothermic, and that with ethylenediamine was exothermic. Ethylenediamine presented a stronger binding constant value for CoTPP, so it was considered as a potential agent for SO2 removal.