There is a lack of detailed research on the production of isoprene and D-limonene by solid base-catalysed thermal depolymerization of waste tires (WTs). This work aimed to investigate the thermal decomposition characteristics, reaction kinetics, high value-added products production and potential mechanisms during WT pyrolysis in the presence of calcium oxide (CaO) via Thermogravimetry-Fourier Transform Infrared spectrometer (TG-FTIR) and Pyrolyzer-Gas Chromatography/Mass spectrometry (Py-GC/MS). The results obtained from TG indicated that CaO accelerated depolymerization in terms of reducing the reaction temperature, which is also reflected in the kinetic parameters. It can be found that the content of D-limonene increased by 13.76% and that of isoprene increased by 37.57%, which were attributed to differences in the depolymerization mechanisms in the presence of CaO. Furthermore, CaO had a profound impact on desulfurization by reducing benzothiazole, sulfoacid, and thiophene. The potential catalytic mechanisms of isoprene and D-limonene production and desulfurization were also proposed. This work deepens the understanding of the catalytic pyrolysis of WT under CaO and unambiguously demonstrates the great potential of CaO in enhancing isoprene and D-limonene production, providing new insight for the cleaner production of high value-added products from WT.