The development of highly stable and strongly active electrode materials for sodium‐ion batteries (SIBs) and overall water splitting (OWS) is critical in sustainable energy storage and conversion systems. Here, a new electrode material N‐Fe‐C@Nb2CTx is introduced, with a layered sandwich structure consisting of N‐doping Fe‐MOF derived‐nanorods (Fe‐C) and Nb2CTx MXenes. Specifically, Nb2CTx obtained by etching Nb2AlC with HF acid is used as the main body to construct the layered sandwich structure with Fe‐C as the filler. Benefiting from this structure, Fe‐MOF grows in situ within Nb2CTx, which restrains MXenes aggregation and stacking and also alleviates the bulk effect of sodium‐ion embedding/de‐embedding, thus improving its stability. Again, the more exposed active sites from the layered sandwich structure and N‐doping introduction ensure high reactivity as electrode materials. In addition, Fe‐C nanorods strengthen the linkage between the Nb2CTx layers and N‐doping enhances the ion/electron transport rate, thereby boosting the effective mass transfer and electrical conductivity. Density functional theory (DFT) calculations show that Fe‐C and N‐doping help increase the density of states (DOS) and material electrical conductivity. Meanwhile, the generated oxygen species (*OH and *O) in OER are captured by in situ FT‐IR test. As a result, the N‐Fe‐C@Nb2CTx electrochemical test displays good electrochemical performance in SIBs and OWS.