Thermal annealing polymeric membranes consisting of thermally saccharide labile units have been proven to be a feasible approach to produce highly permeable gas separation membranes. In this work, thermal labile units with different molecular weights and structures, glucose (180 g/mol), sucrose (342 g/mol) and raffinose (504 g/mol), are chosen to be grafted onto the side chains of a polyimide and the membranes are annealed to investigate the effects of thermally labile units on its properties. The gas separation performance of the membranes for various gases such as O-2, N-2, CO2, CH4, C2H6, C3H6 and C3H8 are examined. It is observed that when the grafted and annealed membranes are annealed from 200 to 400 degrees C, a substantial increase in gas permeability is achieved with moderate gas-pair selectivity. It could be attributed to the formation of microvoids upon the degradation of the thermally labile unit. Depending on the thermally labile unit grafted, a four to eight-fold increase in gas permeability was seen. The variation of the gas separation performance with the thermally labile unit is elucidated by the thermal decomposition behavior of the thermally labile units and the interaction with the polymer matrix. The membrane resistance to CO2 plasticization is also investigated. The annealed membranes show good flexibility with enhanced gas permeability and CO2 plasticization resistance. The membranes exhibit excellent CO2/C2H6 and C3H6/C3H8 separation performance. The selectivity for CO2/C2H6 is over 34. The separation performance for O-2/N-2, CO2/N-2 and CO2/CH4 gas pairs fall slightly below the upper bound. The CO2 permeability of the membrane grafted with glucose declines slightly from 1389 Barrers to 1339 Barrers while maintaining the same CO2/CH4 selectivity of about 26.6 when subjected to a binary gas mixture. (c) 2012 Elsevier B.V. All rights reserved.