The invention discloses a near infrared up-conversion long afterglow luminescent material and a preparation method thereof. The preparation method comprises the following steps: (1) weighing raw materials, and evenly mixing raw material powder, wherein the raw materials comprises a raw material A, a raw material B, a raw material C, and a raw material D, the raw material A is chromium oxides or corresponding salts, the raw material B is oxides of erbium or thulium or corresponding salts, the raw material C is ytterbium oxides or corresponding salts, and the raw material D is oxides of zinc, gallium/aluminum, or germanium/tin or corresponding salts; and (2) pressing and moulding mixed powder obtained in the step (1) to obtain a blank sample; (3) solid-phase sintering the blank sample obtained in the step (2) at a high temperature; and (4) cooling the sintering product to obtain the target material. A high temperature solid phase method is adopted, the prepared material, which is doped by Cr<3+> and Er<3+>/Tm<3+> and takes Yb<3+> as the sensitizing agent, has a near infrared excited up-conversion luminescence function and a super long time afterglow performance and can be used as a high performance functional material applied to related fields.