To tolerate high processing temperature during the fabrication of low-temperature polycrystalline silicon thin-film transistors (LTPS-TFT) in flexible OLED devices, the polyimide (PI) films, which are used as substrate, should have ultra-high glass transition temperature (T g > 450 C) and ultra-low coefficient of thermal expansion (CTE at 0-5 ppm K À1 ). In this paper, two novel heterocyclic monomers, namely, N,N'-(xanthone-2,7-diyl)bis(4-aminobenzamide) (p-DAXBA) and N,N'-(xanthone-2,7-diyl)bis(3-aminobenzamide) (m-DAXBA), which contain a xanthone moiety, are prepared and polycondensed with pyromellitic dianhydride (PMDA), respectively. PI films (PIa and PIb) with intrinsic high T g and low CTE are designed from the perspective of rigid conjugate xanthone structure and hydrogen bonding interaction. It is found that the PIa films prepared by p-DAXBA have better linear structure of molecular chains and show relatively higher T g and lower CTE. The T g of PIa-40 is greater than 450 C, and CTE can reach as low as 2.7 ppm K À1 , tensile strength of 179 MPa, modulus of 5.67 GPa, indicating potential application prospect as a flexible OLED substrate.