To solve the problems of high cost and low efficiency of conventional co-production system of hydrogen and electricity with low hydrogen-to-electricity ratio, a novel co-production system based on coal partial gasification with CO2 capture is proposed and thermodynamically analyzed. The new system integrates the conceptions of cascade conversion of coal and cascade utilization of syngas to realize the system with high efficiency, low cost, environmental friendliness and flexible hydrogen-to-electricity ratio. The performance of the new system is evaluated by an Aspen Plus model and effects of the operating conditions are also studied. It is found that the system with capturing CO2 of 59.7% and hydrogen-to-electricity ratio of 4.76 holds a high exergy efficiency of 54.3% when the carbon conversion ratio of the pressurized fluidized bed (PFB) gasifier is equal to 0.7. The carbon conversion ratio of the PFB gasifier is a dominant factor to decide the performance of system. In comparison with the series-type co-production system, the parallel-type co-production system and separate production system, the new system proposed in this study has exergy-saving efficiency of 17.7%, 15.1% and 8.9%, respectively.