The invention relates to a 5-methyl-1H-tetrazole/1,2,3-trimesic acid mixed ligand cobalt (II) complex magnetic material, and a preparation method and application thereof. The chemical formula of the complex magnetic material is [Co2(H2O)(mtz)(btc)], wherein mtz is a 5-methyltetrazole -1-valent anion, and btc is a 1,2,3-trimesic acid -3-valent anion. The complex magnetic material is prepared by a hydrothermal method, and has the advantages of high yield and favorable repeatability. The complex magnetic material is a cobalt (II) complex simultaneously containing 5-methyl-1H-tetrazole 1,2,3-trimesic acid mixed ligand; and the complex magnetic material has obvious spontaneous magnetization behavior at low temperature, and has huge application value as a molecule-base magnetic material in the field of material science.