Abstract Al–Mn alloys with Mn content ranging from 0 to 15.8 at.% are prepared by electrodeposition from an ionic liquid at room temperature, and exhibit a remarkably broad range of structures. The alloys are characterized through a combination of techniques, including X-ray diffraction, electron microscopy and calorimetry. For alloys with Mn content up to 7.5 at.%, increasing Mn additions lead to a decrease in grain size of single-phase microcrystalline face-centered cubic (fcc) Al(Mn). Between 8.2 and 12.3 at.% Mn, an amorphous phase appears, accompanied by a dramatic reduction in the size of the coexisting fcc crystallites to the ∼2–50 nm level. At higher Mn contents, the structure nominally appears entirely amorphous, but is shown to contain order in the form of pre-existing nuclei of the icosahedral quasicrystalline phase. Additionally, nanoindentation tests reveal that the nanostructured and amorphous specimens have very high hardnesses that exhibit complex trends with Mn content.