A series of copolyimides were prepared by thermal imidization of poly(amic acid)s (PAAs) derived from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3′,3,4′-biphenyltetracarboxylic dianhydride (a-BPDA), p-phenylenediamine (PDA) and 4,4′-oxydialinine (4,4′-ODA) commonly used for the production of commercial polyimides. The flexible copolyimide films were obtained from that the molar ratio of s-BPDA, a-BPDA, PDA and 4,4′-ODA was 9:1:8:2 (Co-PIs-3), 8:2:9:1 (Co-PIs-5) and 8:2:8:2 (Co-PIs-6). These obtained copolyimide films were characterized by Fourier transform-infrared spectroscopy(FT-IR), wide angle X-ray (WAXD), Thermogravimetric (TG), dynamic mechanical thermal analysis (DMA), thermomechanical analysis (TMA), field-emission scanning electron microscopy (FE-SEM) and mechanical properties measurement. The results showed that three copolyimides remained semi-crystalline and exhibited high glass transition temperature (T g ), high thermal stability, great ultimate tensile strength and low coefficient of thermal expansion (CTE). The Co-PIs-5 had lower crystallinity, lower CTE, greater elongation at break, higher T g and thermal stability and the greater dense extent, compared with Co-PIs-3 and Co-PIs-6. Structure and property relations of the prepared polyimides were also briefly discussed. The results revealed that the copolymerization of s-BPDA/PDA with a small number of 4,4′-ODA/a-BPDA was a useful means for enhancing flexibility without sacrificing low CTE.