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A new oxide, LaMn3Ni2Mn2O12, was prepared by high-pressure and high-temperature synthesis methods. The compound crystallizes in an AA'3B2Bi2O12-tYPe Ai siteand B site ordered quadruple perovskite structure. The charge combination is confirmed to be LaMn33+Ni2 2Mn24+O12, where La and Mn3+ are 1:3 ordered at the A and A' sites and the Ni2+ and Mn4+ are also distributed at the B and B' sites in an orderly fashion in a rocksalt-type manner, respectively. A G-type antiferromagnetic ordering originating from the A'-site Mn3+-sublattice is found to occur at T-N approximate to C-Z% 46 K. Subsequently, the spin coupling between the B-site Ni' and B+-site Mn4+ sublattices leads to an orthogonally ordered spin alignment with a net ferromagnetic component near T-C approximate to 34 K First-principles calculations demonstrate that the A'-site Mn" spins play a crucial role in determining the spin structure of the B and B' sites.