As SO2 removal via traditional aqueous amine scrubbing requires large amounts of energy for absorbent regeneration, phase-change absorption was considered to be a promising alternative, as regeneration of only the SO2-rich phase is needed. The SO2-lean phase can be directly reused, thus greatly reducing energy requirements. We herein investigated the phase change absorption behavior of N,N,N',N'-tetramethyl-p-phenylenediamine (TPD) in organic solvents. In general, the TPD absorption rate in organic solvents followed the order: dimethylformamide > diethylene glycol dimethyl ether > propylene carbonate > butanol, which is related to their Henry's constant. Our results indicated that TPD reacted with SO2 to form the charge-transfer complex TPD:SO2, which was further converted into TPD center dot 2SO(2) upon increasing the absorption time. Furthermore, the addition of H2O promoted the formation of TPD center dot 2SO(2), but it exhibited a negative effect on the absorption rate. Moreover, in the presence of O-2 and H2O, TPD-SO2 in solution was converted slowly into [H2TPD][HSO4](2)center dot TPD center dot SO, decomposed into TPD and SO2 at similar to 100 degrees C and exhibited a relatively stable recyclability for SO2 absorption. At last, TPD.SO, was used as a surrogate of SO2 to synthesize sulfonamide; its activity was higher than that of a reported complex of triethylenediamine and SO2.