The invention provides compositions and a preparation method of an extra-large mode area metaphosphate optical fiber, and belongs to the technical fields of optical materials and laser. The invention solves the problem that an optical fiber cannot meet a mode field with the diameter of over 100 mu m and single-mode transmission characteristic simultaneously in the prior art. The metaphosphate optical fiber comprises a fiber core consisting of phosphorus pentoxide, alumina, potassium oxide, barium oxide, calcium oxide, magnesium oxide and rare earth oxide in a certain molar percent, and a fiber core clad layer consisting of phosphorus pentoxide, alumina, potassium oxide, barium oxide, calcium oxide and magnesium oxide in a certain molar percent. The prepared fiber core preformed rod and clad layer preformed rod are sleeved and fused, and are subjected to surface processing and drawing treatment so as to form the metaphosphate optical fiber. The metaphosphate optical fiber has excellentthermal property, optical property, mechanical property and mechanical performance.