Al82Fe16Ce2 and Al82Fe14Mn2Ce2 amorphous alloys were successfully synthesized by the mechanical alloying technique. The microstructural evolution of the milled powders was thoroughly investigated employing X-ray diffraction (XRD) and scanning electron microscopy (SEM). Additionally, their magnetic properties were quantitatively evaluated by a vibrating sample magnetometer (VSM). A full amorphous structure was obtained for both alloys after milling for 40 h. During the initial milling stage, extending from 5 to 20 h, an fcc solid solution phase was formed, coexisting with the residual Al phase. The partial substitution of 2 atomic percent (at.%) Mn for Fe in Al82Fe16Ce2 did not affect the alloy’s glass-forming ability. The amorphous Al82Fe16Ce2 and Al82Fe14Mn2Ce2 powders exhibited a nearly spherical shape, with diameters ranging from 1 to 3 µm and to 10 µm, respectively. Additionally, both the Al82Fe16Ce2 and Al82Fe14Mn2Ce2 alloys demonstrated characteristics of hard magnetism.