The invention provides a mixed ligand manganese supermolecular polymer with yellow fluorescence. The supermolecular polymer has the chemical composition general formula of {[Mn(Hbtot)(phen)](H2O)}n, belongs to a triclinic crystal system, has the space group of P-1, and has cell parameters: a=10.262(5) angstroms, b=12.566(6) angstroms, c=14.893(8) angstroms, and F=1748.1(15) angstrom<3>; Hbtot<2->is obtained by removing two protons from semi-rigid ternary organic carboxylic acid H3btot, and the structure of the H3btot is represented by the formula I; the phenanthroline phen structure is represented by the formula II. The yield of the mixed ligand manganese supermolecular polymer having yellow fluorescence and prepared by the method provided by the invention reaches about 75%, and the supermolecular polymer can be used as fluorescent probes for part of anions, cations and solvent micromolecules.