The invention discloses an X-ray fluorescence spectroscopy analysis fusion sample preparation method of an aluminum, manganese, calcium and iron alloy, which comprises the steps of: firstly, coating a uniform protection wall layer in a platinum crucible by using lithium tetraborate, then placing an aluminum, manganese, calcium and iron sample, an oxidizing agent, a lithium borate solvent and a releasing agent into the platinum crucible in which the protection wall is coated, uniformly mixing, and then pre-oxidizing the aluminum, manganese, calcium and iron sample; and finally, melting the pre-oxidized aluminum, manganese, calcium and iron sample, and cooling to obtain an aluminum, manganese, calcium and iron sample glass fuse piece, wherein the aluminum, manganese, calcium and iron sample is a detection sample or calibration sample of the aluminum, manganese, calcium and iron alloy, and the sample glass fuse piece is a detection sample glass fuse piece or calibration sample glass fuse piece of the aluminum, manganese, calcium and iron alloy. On the premise of no corrosion to the valuable platinum crucible, the glass fuse piece can be prepared, and the prepared sample is excellent and uniform, thus the mineral effect and the grain size effect are completely eliminated.