The invention discloses a preparation method of a multilayer structured high-temperature superconductive thick film. The structure of the high-temperature superconductive thick film includes YBCO (polymine)/Y(Dy)BCO/manganese copper oxide/magnesium oxide/magnesium oxide/yttrium oxide/alumina/a Hastelloy belt. According to the invention, Dy is added to the first superconductive layer, the pinning force is enhanced, and good basis is provided for development of the superconductive layer later; polymine (PEI) is added from the second layer, Cu2+ makes complexation reaction with the PEI, volatilization of the Cu2+ in the low-temperature pyrolysis stage is reduced, a segregation phenomenon of the Cu2+ can be inhibited effectively, and a phenomenon that the surface of the thick film tends to crack can be avoided to certain extent; a dip-coating method is used for coating for multiple times, and low-temperature processing and intermediate-temperature processing are carried out; and via stepped low-temperature thermal decomposition and one-step high-temperature sintering, a multilayer structured ReBCO thick film which has no cracks in the surface, includes a double-axis texture and has excellent grain orientation is prepared successfully, and in the Hastelloy buffer layer, the critical current density can still reach 1.4MA/cm2 (77K, 0T) and Ic reaches 140A/cm after thickness conversion.