The invention relates to a single-mode optical fiber with ultralow loss and large effective area and a preparation method thereof. The optical fiber sequentially comprises an inner core layer, a sunken core layer, an outer core layer, an inner cladding layer, a sunken cladding layer and an outer cladding layer from inside to outside, wherein the inner core layer, the sunken core layer, the outer core layer, the inner cladding layer and the sunken cladding layer take silicon dioxide as a substrate material and are added with a dopant, and the outer cladding layer is pure silicon dioxide; and wherein the relative refractive index of the inner core layer is delta n1, the relative refractive index of the sunken core layer is delta n2, the relative refractive index of the outer core layer is delta n3, the relative refractive index of the inner cladding layer is delta n4, the relative refractive index of the sunken cladding layer is delta n5, and the magnitude of the relative refractive indexes are as follows: delta n1>delta n3>delta n2>delta n4>delta n5, and the material is prepared by adopting an MCVD process and an OVD process. The optical fiber of the invention has good comprehensiveperformances such as effective area, cut-off wavelength, attenuation, dispersion, bending loss and the like.