The invention discloses a method for preparing hexyl-dioctyl phosphorus oxide. The method comprises the following steps: adding dioctyl phosphorus oxide, 1-hexene, an acetic acid solvent and di-tert-butyl peroxide in a PTFE (Polytetrafluoroethylene) reaction kettle, adding a small amount of industrial mixed decene, stirring and dissolving, rising the temperature to be 130 to 140 DEG C, reacting for 12 to 36 hours, detecting and completely reacting under <31>P-NMR (Nuclear Magnetic Resonance), adding 5 to 15 weight percent of diluted hydrochloric acid in a reaction solution for carrying out demulsifying and washing, extracting by using trichloromethane, washing an organic layer to be neutral by using water, evaporating to remove trichloromethane and unreacted olefin through a rotary evaporator, recrystalizing by using ethanol, filtering, and carrying out vacuum drying, thus obtaining white solid. The method for preparing hexyl-dioctyl phosphorus oxide, disclosed by the invention, is simple in steps, is green and environmentally friendly and is good in atom economy, a product is high in purity, separation is easy, and an industrial prospect is obtained; the product is applied to industries of water quality detection and sewage treatment.