The bulk properties of P 4 3 32 LMNO and its intrinsic defect chemistry have been investigated using DFT. To correctly capture the magnetic properties and ground state electronic structure, we demonstrated the importance of a systematic evaluation of the magnetic or- A comprehensive analysis of the defect chemistry over all growth conditions shows a tendency toward O-poor (n-type) conditions where Mn 3+ formation is encouraged. This may explain why many experimental studies find it challenging to study solely the effect of Mn/Ni ordering on the electrochemical performance. Our work provides insights into the complex defect chemistry of LMNO which can be utilised when developing synthesis methods to fine-tune electrochemical performance. This knowledge is also crucial for understanding the charge compensation mechanisms with the presence of extrinsic defects.