The invention relates to the field of lithium batteries, and discloses a lithium ion solid electrolyte with a core-shell structure and a preparation method. The preparation method comprises the following steps of (1) mixing Li2CO3, Al2O3, TiO2 and NH4H2PO4, calcining, cooling, grinding and sieving to obtain core layer powder; (2) adding LiOH H2O, H3BO3, NH4H2PO4 and NH4F into deionized water, uniformly stirring, adjusting the pH value, adding silica sol, and mechanically stirring to obtain sol; and (3) adding the core layer powder and Al (H2PO4) 3 into the sol, carrying out spray drying, sintering the obtained precursor material, cooling, grinding, washing, and drying to obtain the lithium ion solid electrolyte with the core-shell structure. Compared with a common inorganic solid electrolyte, the inorganic solid electrolyte with the core-shell structure has the advantages that a complete and compact electron shielding layer is formed on the surface of a base material, so that an electrochemical window is wide, the ionic conductivity is high, and the application prospect is good.