O3-type NaNi0.5Mn0.3Co0.2O2 based positive electrode materials are very promising for sodium-ion batteries. However, the irreversible phase transition due to structural deformation leads to sluggish kinetics, rapid capacity fade, and low C-rate performance, limiting its wide practical applications. The partial substitution of Co3+ (0.545 Å) by Al3+ (0.535 Å) ions in the transition-metal layer in NaNi0.5Mn0.3Co0.2-xAlxO2 (0.01 ≤ x ≤ 0.02) is an effective strategy to address the issue of structural deformation and thus to improve the electrochemical performance of NaNi0.5Mn0.3Co0.2O2 cathode. Solution combustion synthesis of NaNi0.5Mn0.3Co0.2-xAlxO2 (x = 0.01, 0.02) shows O3-type structure of NaNi0.5Mn0.3Co0.2−xAlxO2 material with the space group of R3¯m. The composition with an overall x = 0.02 Al doping delivers an initial 120 mAh g−1 capacity at a 0.1 C rate. It retains 90 % capacity even after 200 cycles than the other stoichiometric aluminum substitution, x = 0.01 (77 %). Moreover, the NaNi0.5Mn0.3Co0.18Al0.02O2 shows a good capacity of ~ 83 mAh g−1 even at a high C-rate of 5 C, almost 70 % of the initial capacity at the 0.1 C rate. The Al-substitute NaNi0.5Mn0.3Co0.2−xAlxO2 cathode's electrochemical performance is attributed to the enhancement in the structural stability of the sodium layered transition metal oxide after the partial substitution of Co3+ by Al3+ ion. Finally, the practical sodium-ion full cells are realized using a hard carbon-based anode and NaNi0.5Mn0.3Co0.18Al0.02O2 cathode, showing 91 % capacity retention at the end of 100th cycles with an OCV of 3.5 V. © 2022 Elsevier B.V.