A composition of and a method of making high performance mixed matrix hollow fiber membranes is described. The membranes have a high resistance to plasticization by use of a predetermined amount of crosslinking. The preferred polymer material for the membrane is a polyimide polymer continuous phase comprising ester crosslinks and a molecular sieve material dispersed within the polymer continuous phase. The resultant mixed matrix hollow fiber membrane exhibits a high permeance of CO2 in combination with a high CO2/CH4 selectivity. Another embodiment provides a method of making the mixed matrix hollow fiber membrane from a monesterified polymer followed by final crosslinking after hollow fiber formation.