The present invention discloses a new type of polyimide membrane with high permeances and high selectivities for gas separations and particularly for CO2/CH4 and H2/CH4 separations. The polyimide membranes have CO2 permeability of 50 Barrers or higher and single-gas selectivity for CO2/CH4 of 15 or higher at 50°C under 791 kPa for CO2/CH4 separation. The polyimide membranes have UV cross-linkable functional groups and can be used for the preparation of UV cross-linked polyimide membranes having CO2 permeability of 20 Barrers or higher and single-gas selectivity for CO2/CH4 of 35 or higher at 50°C under 791 kPa for CO2/CH4 separation.