Carbon felt (CF) and activated carbon (AC) based electrodes for sodium polysulfide/bromine redox flow battery (PSB) were prepared and compared with a laboratory scale PSB flow cell in terms of structure and application performances. The structural properties of the two types of electrodes were characterized by filamentary analog and BET analysis, respectively. Catalyst coating, discharge behavior analysis and thermogravimetric analysis-mass spectrometry (TG-MS) were carried out to make out the different dominant factor in the application performances of the two materials. Compared to AC based electrode (ACE), despite of the relatively low surface area, CF demonstrates almost the same application performances, much more gains in electrochemical activity towards negative half-cell reactions by catalyst coating, and more even discharge voltage curve and stable cycling performance. At current density of 40mAcm−2, an average energy efficiency of up to 81% over 50 cycles (about 600h) has been achieved with cobalt coated CF, but with ACE only 64.7% within 16 cycles, which decreases quickly due to the loss of surface area resulted from sulfur depositing. The difference in structure related to mass transport makes the application performances gap between the two types of materials in PSB.