Three new GC derivatives, carbonic acid bis-(2-oxo-[1,3]dioxolan-4-ylmethyl) ester (CABE), succinic acid bis-(2-oxo-[1,3]dioxolan-4-ylmethyl) ester (SABE) and terephthalic acid bis-(2-oxo-[1,3]dioxolan-4-ylmethyl) ester (TABE), were designed and synthesized. We investigated the thermal stability and the thermal pyrolysis of three compounds by TG–FTIR, and the bond dissociation energy was calculated to further demonstrate the decomposition process. The results showed that the three GC derivatives had one, two, three weight loss stages, respectively. Their initial decomposition temperature was as high as 200°C, which means that the compounds have good thermal stability. 5% weight loss temperature was increased in the order of TABE>SABE>CABE. In thermal pyrolysis process, the CC, CO bonds of cyclic carbonate fractured preferentially, and then the CO bonds nearby cyclic carbonate of SABE and TABE continued to fracture to produce linear ester in the form of fragment.