The invention belongs to the technical field of medicines, and particularly relates to a camptothecin-based dimer compound as well as preparation and application thereof. The dimer compound has a structure represented by a formula (I), wherein in the formula (I), m is an integer of 1-4, and n is an integer of 1-4. The dimer compound is connected with camptothecin and immunomodulatory small molecules NLG919 through reductive disulfide bonds, so that combination of tumor chemotherapy and immunotherapy is realized, and the anti-tumor curative effect is enhanced. The compound prepared by the invention can be reduced into original camptothecin and NLG919 under a reducing condition, has good anti-tumor activity in tumors such as liver cancer, breast cancer, colon cancer, melanoma, ovarian cancerand the like, and can be used for inhibiting the activity of indoleamine 2,3-oxygenase, increasing DC cell maturation and reducing the number of immunosuppressive Treg cells; the drug resistance of tumor stem cells to camptothecin is reduced, and the tumor immune response is enhanced.