Identification of gaseous decomposition products from irreversible side-reactions enables understanding of inner working of rechargeable batteries. Unlike for Li-ion batteries, the knowledge of the gas-evolution processes in Na-ion batteries is limited. Therefore, in this study, we have performed online electrochemical mass spectrometry to understand gassing behavior of model electrodes and electrolytes in Na-ion cells. Our results show that a less stable solid–electrolyte interphase (SEI) layer is developed in Na-ion cells as compared with that in Li-ion cells, which is mainly caused by higher solubility of SEI constituents in Na-electrolytes. Electrolyte reduction on the anode has much larger contribution to the gassing in the Na-ion cells, as gas evolution comes not only from direct electrolyte reduction but also from the soluble species, which migrate to the cathode and are decomposed there. During cell cycling, linear carbonates do not form an SEI layer on the anode, resulting in continuous electrolyte reduction, similar to Li-ion system but with much higher severity, while cyclic carbonates form a more stable SEI, preventing further decomposition of the electrolyte. Besides the standard electrolyte solvents, we have also assessed effects of several common electrolyte additives in their ability to stabilize the interphases. The results of this study provide understanding and guidelines for developing more durable electrode–electrolyte interphase, enabling higher specific energy and improved cycling stability for Na-ion batteries.