Three aromatic polyimides (PIs) were prepared from a new aromatic diamine monomer derived from the rigid ring dibenzofuran. All PIs were obtained in high yield and the inherent viscosities were in the range of 0.60 and 0.74 dL g(-1). Polyimides derived from 4,4'-hexafluoroisopropyliden diphthalic anhydride (6FDA) and 4,4'-(dimethylsilanediyl) diphthalic anhydride (SiDA) showed excellent solubility in a variety of aprotic polar organic solvents. All PIs showed high thermal stability with thermal decomposition temperature (TDT10%) between 555-590 degrees C and the glass transition temperatures (T-g) values were between 290 and 315 degrees C. Polymeric films were obtained from PI-6FDA and PI-SiDA solutions and then contact angle and surface free energy were tested in order to know the hydrophobicity of materials. Likewise, permeability and selectivity analyses were developed where PI-6FDA film offered a reasonably acceptable balance of permselectivity with values close to the Robeson upper-bound (1991), in particular for the CO2/CH4 gas pair.