Electrolytic oxygen generation system (EOGS) is the only system that can provide oxygen for astronauts in a physicochemical regenerative way in a long-term manned spacecraft. In order to ensure that the astronauts in the cabin can obtain a continuous and enough oxygen supply, it is necessary to carry out real-time condition monitoring and fault diagnosis of the EOGS. This paper deals with condition monitoring and fault diagnosis of the EOGS. Firstly, the dynamic model of the system is established based on the principle electrolysis for actual oxygen production system and the state observer of the system has been designed by using unscented Kalman filter (UKF). The total pressure in the cabin and the partial pressure of oxygen in the electrolytic cell can be observed. Then, considered the actual conditions of the manned space mission with one more astronaut, i.e., 3 astronauts, the simulation experiment is carried out. The simulation results show that the method can effectively estimate the system state, and it is of great significance to ensure the normal operation of the electrolytic EOGS system in the space station.