The invention relates to a solid electrolyte, and discloses a composite solid electrolyte and a preparation method thereof, and a lithium storage battery. The composite solid electrolyte comprises a negative electrode side electrolyte layer, an ion dispersion layer and a positive electrode side electrolyte layer which are sequentially attached and compressed, the negative electrode side electrolyte layer is a PEO electrolyte membrane layer, the ion dispersion layer is Li3N, the positive electrode side electrolyte layer is a polymer solid electrolyte membrane layer, so that the lithium ion conductivity of the composite electrolyte is improved, the deposition uniformity of lithium ions in the charging process is improved, the lithium dendritic crystal forming rate is low, the cycle life of the lithium metal negative electrode is prolonged, and the cycle life of solid-state lithium storage is further prolonged; and the material still has a relatively high performance retention rate aftermultiple cycles.