©2020 IOP Publishing Ltd.The structural and magnetic properties ofMg/Mn-doped ZnO were investigated by the firstprinciples study and Monte Carlo methods (MCs). Applying magnetic force theorem (MFT) and using Kohn-Sham orbitals in the GGA-PBE scheme, the exchange coupling parameters (J) were calculated to figure out the magnetic interactions between atomic sites. Mn-Mg volume clustered (C1) ferromagnetic (FM) state was preferred; herewith, the calculated magnetic moment ofMnwas 4.19μB andMghas the highest moment value when clustered withMnions. NearestMnions interacted antiferromagnetic (AFM) despite the increasing distance lead them to be in FM. However,AFM/FM wasoriginated from the p-d hybridization, superexchange interaction and direct exchange between distantMnions. In addition, the Curie temperature (Tc) was calculated as 311K using averaged magnetization and magnetic susceptibility via MC.