To investigate the pyrolysis characteristics of waste tire, an analytical pyrolyzer coupled with gas chromatography/mass spectrometry (Py-GC/MS) setup had been proposed. Waste tire was pyrolyzed under different temperatures. Results showed that the primary pyrolysis products of waste tire at 600 degrees C were alkenes rather than alkanes or aromatics. Isoprene (18.7%) and D-limonene (22.9%) represented the main compounds of chain alkenes and cyclic alkenes, respectively. The degradation procedure of D-limonene was also investigated. It could be indicated that, when the temperature was 500 degrees C and below, isomerized alkenes of D-limonene were the main products. With the temperature increasing to 600 degrees C and above, aromatics began to raise. According to the product distribution, eight pyrolysis reaction pathways of D-limonene were proposed. Pyrolysis of waste tire under different temperatures proved that the reaction pathways of D-limonene were reliable. Moreover, a thermogravimetric analyzer coupled with Fourier transform infrared spectroscopy (TG-FTIR) investigation also consolidated the main processes proposed by Py-GC/MS. These findings provide some references for the pyrolysis mechanism of waste tires.