Structures and electrochemical performances of Na-rich layered cathode Na2RuO3 are studied by substitution of Zr for Ru. Na2Ru0.95Zr0.05O3 exhibits a combination of disordered and ordered stacking state with a weight fraction of ∼61.57% and 38.43%, respectively. The disordered and ordered Na2Ru0.95Zr0.05O3 exhibits reversible capacity of 137 mAh g−1 that is consistent with the theoretical capacity at a current density of 1 C. In addition, the material shows good cyclability with a capacity retention of 77% after 200 cycles at current density of 1 C, and the Coulombic efficiency remains at about 99% during cycling. The structural evolutions of the Na-rich layered Na2Ru0.95Zr0.05O3 during de(sodiation) have been investigated and found to proceed via a biphasic mechanism.