This study was conducted to evaluate the characterization of the pyrolysis products of propylene glycol(PG) and glycerine alone and together with tobacco. The weight change of the samples during the pyrolysis was measured by a thermal analyzer(STD-2960). The pyrolysis products were determined by GC/MS after pyrolysis using a curie-point pyrolyzer(CPP, $220^{\circ}C,\;420^{\circ}C,\;650^{\circ}C,\;and\;920^{\circ}C$) and a double-shot pyrolyzer(DSP, $220^{\circ}C,\;420^{\circ}C,\;650^{\circ}C,\;and\;800^{\circ}C$), respectively. The pyrolysis products from tobacco with and without the addition of PG($2\%$) and glycerine($2\%$ were assayed for its pyrolytic behavior. The results showed that a dramatic change in weight of PG and glycerine was observed at $175^{\circ}C\;and\;249^{\circ}C$, respectively. PG and glycerine showed different patterns for their pyrolysis products according to the method of pyrolysis. Namely, the change rate in pyrolysis with DSP was much higher than that of CPP at above $650^{\circ}C$. The major pyrolysis products of PG were propene, acetaldehyde, propanal, and acetol; the major pyrolysis products of glycerine were 2-propenal, 2-propenol, acetol, and acetic acid. In the pyrolysis experiments of tobacco added PG and glycerine, the pyrolysis products of PG and glycerine weren't detected additionally, except for diethyleneglycol diacetate. From these results, it can be concluded that the PG and glycerine added to tobacco would not be expected to pyrolyse extensively during smoking.