The two B-site ions Mn 3+ and Mn 4+ in the stoichiometric spinel structure LiMn 2 O 4 form a complex, columnar ordered pattern below the charge-ordering transition at room temperature. On further cooling to below 66 K, the system develops long-range antiferromagnetic order. In contrast, whereas lithium-substituted Li͓Mn 2−x Li x ͔O 4 also undergoes a charge-ordering transition around room temperature, it only displays frozen in short-range magnetic order below ϳ25-30 K. We investigate to what extent the columnar charge-order pattern observed in LiMn 2 O 4 can account for the measured magnetic ordering patterns in both the pure and Li-substituted ͑x = 0.04͒ compounds. We conclude that eightfold rings of Mn 4+ ions form the main magnetic unit in both compounds ͑x = 0 , 0.04͒, and that clusters formed out of these rings act as superspins in the doped compound. The ground state properties of the known lithium-based cubic spinel compounds LiT 2 O 4 range from BCS superconductivity 1 ͓T =Ti͔, via heavy fermion behavior 2 ͓T =V͔ to frustrated antiferromagnetism 3,4 ͓T =Mn͔. In these systems, the divalent B-site ions ͑3+ and 4+͒ have an octahedral oxygen surrounding, while the Li + ions occupy the A-sites. In this paper we focus on the magnetism in the Mn compound. Above ϳ300 K, LiMn 2 O 4 is an electronhopping conductor, and the system undergoes a chargeordering ͑CO͒ transition on cooling down. Similar to the CO transition in magnetite, 5 the B-site octahedra are slightly deformed and a structural transition accompanies the CO transition. However, unlike for magnetite, the Mn 3+ -Mn 4+ charge-ordered structure has ͑most likely͒ been resolved by In stoichiometric LiMn 2 O 4 the Mn 3+ ions line up in columns along the c-axis 6 when cooled to below 300 K, see Fig. 1͑a͒. Multiple types of Mn 3+ sites can be distinguished. One type is located in cubes of four Mn 3+ ions and four O 2− ions ͑Mn-O distance= 2.05 Å͒ stacked along the c-direction. These cubes are at the center of eightfold rings of Mn 4+ ions. The Mn 4+ ions within these rings couple antiferromagnetically ͑AF͒ to each other through a 90°Mn-O-Mn exchange. The spaces in between neighboring rings are filled with the other types of Mn 3+ ions, which thus form columns in the c-direction. The unit cell ͑a = 24.74 Å, b = 24.84 Å, and c = 8.20 Å͒ houses eight eightfold rings. 6 The Mn 4+ rings only interact with other rings via the intervening Mn 3+ ions. When cooled to below 66 K, AF ordering develops, 7 but the ordered structure has not been resolved yet.The Li-doped material Li͓Mn 2−x Li x ͔O 4 has also been studied in detail 3,4 because of its applications as a battery material. 8 When a small amount of Li is substituted on the Mn sites, the material retains its capacity for removal of Li from the A-sites without affecting the overall spinel structure ͑hence its use in lithium batteries͒, but the ϳ300 K structural phase transition no longer takes place, even though the CO transition is unaffected. ͑Suppression of the structural transition greatly enhances the lif...