The invention discloses a preparation method of a symmetric phosphine oxide type TADF organic photoelectric material, and belongs to the field of organic functional materials. 2, 2 '-dinitro-biphenyl is subjected to stannous chloride reduction, amido acylation, electricity-rich aromatic ring bromination reaction and acid deacylation of a protecting group to form free amido, the amido is converted into 5, 5'-dibromo-2, 2 '-diiodo-biphenyl through a diazonium salt process, then the 5, 5'-dibromo-2, 2 '-diiodo-biphenyl is converted into 5, 5'-dibromo-2, 2 '-diiodo-biphenyl, and the 5, 5'-dibromo-2, 2 '-diiodo-biphenyl is converted into 5, 5 The preparation method comprises the following steps: carrying out lithium-iodine exchange on 2, 2 '-diiodo-biphenyl, carrying out nucleophilic substitution reaction on the 2, 2'-diiodo-biphenyl and dichlorophenylphosphine to generate phenylphosphine heterobenzoindole, oxidizing the phenylphosphine heterobenzoindole to form phenylphosphine oxide heterobenzoindole, and carrying out coupling reaction on brominated aromatic hydrocarbon and heteroaromatic hydrocarbon under the catalysis of copper to synthesize the small organic molecule luminescent material with fluorescent reactive oxygen species. The 2, 8-diphenothiazinyl-5-phenyl benzoxphosphine heteroindole synthesized by the method has the potential of becoming an organic micromolecule electroluminescent material and being used as a photosensitizer for organic photoreaction, and fits the development trend of multifunctional application of organic micromolecule materials.