Herein, the synthesis of new quaternary layered Na-based oxides of the type NaxMnyNizFe0.1Mg0.1O2 (0.67≤ x ≤ 1.0; 0.5≤ y ≤ 0.7; 0.1≤ z ≤ 0.3) is described. The synthesis can be tuned to obtain P2- and O3-type as well as mixed P-/O-type phases as demonstrated by structural, morphological, and electrochemical properties characterization. Although all materials show good electrochemical performance, the simultaneous presence of the P- and O-type phases is found to have a synergetic effect resulting in outstanding performance of the mixed phase material as a sodium-ion cathode. The mixed P3/P2/O3-type material, having an average elemental composition of Na0.76Mn0.5Ni0.3Fe0.1Mg0.1O2, overcomes the specific drawbacks associated with the P2- and O3-type materials, allowing the outstanding electrochemical performance. In detail, the mixed phase material is able to deliver specific discharge capacities of up to 155 mAh g−1 (18 mA g−1) in the potential range of 2.0–4.3 V. In the narrower potential range of 2.5–4.3 V the material exhibits high average discharge potential (3.4 V versus Na/Na+), exceptional average coulombic efficiencies (>99.9%), and extraordinary capacity retention (90.2% after 601 cycles). The unexplored class of P-/O-type mixed phases introduces new perspectives for the development of layered positive electrode materials and powerful Na-ion batteries.