This paper reports the synthesis of a novel cardo type polyimide PI(BTDA-BAPF-DMMDA) based on 3,3',4,4'-benzophenone-tetracarboxylic dianhydride (BTDA), 9,9'-bis (4-aminophenyl) fluorine (BAPF) and 4,4'-biamino-3,3'-dimethyldiphenyl-methane (DMMDA) using the low temperature solution copolymerization method, and cardo polyimide/TiO2 mixed matrix membranes (MMMs) were prepared by blending of TiO2 sol and the PI solution. The incorporation of the cardo groups was achieved through the reaction between the free -COOH of polyamide acid (PAA) and the -NH2 of the BAPF. The chemical structure and physical properties of membrane material were characterized using FTIR, H-1 NMR, DSC and XRD. Results showed that the MMMs containing 24 wt% of TiO2 sol were nano-composite membranes with strong interactions between inorganic TiO2 phase and organic PI phase. Compared with PI(BTDA-DMMDA) membrane, the addition of BAPF and TiO2 greatly improved the gas separation properties of cardo PI membranes and MMMs. The gas permeation (P-O2) and ideal separation factor (a(O2/N2)) of the cardo polyimide PI/TiO2 membrane with a BAPF: BTDA molar ratio of 0.15:1 and TiO2 content of 24 wt% were 4.5 Barrer and 15.8 respectively, which were a respective 9.4 and 4.6 times higher than that of the PI(BTDA-DMMDA) membrane. The P-O2 and a(O2/N2) of the cardo polyimide/TiO2 MMMs prepared in this work were beyond Robeson's trade-off upper bound, highly promising for future gas separation application. (c) 2013 Elsevier B.V. All rights reserved.