The invention provides a preparation method of modified fly ash. In a sealed negative-pressure system, fly ash is adopted as a raw material. When winnowing grading processing is carried out upon the fly ash particles, the graded fine particles and ultra-fine particles are subjected to a chemical-spraying surface modification treatment; the obtained products are heated and dried, such that a target product of the modified fly ash is obtained. According to the modified fly ash provided by the invention, one or more saturated-structure or unsaturated-structure organic groups are bonded on the surfaces of the particles, and an activation index is higher than 0.9. The invention also discloses a fly ash sorting and modifying apparatus. The technical method provided by the invention is energy-saving and environment-friendly, and is advantaged in high utilization rate of fly ash. The obtained modified fly ash is advantaged in wide particle fineness selection range, small dosage of a coupling agent, uniform distribution of the coupling agent, good adaptability with polymer substrates, and the like. In rubber product filling, the modified fly ash can be used for completely replacing calcium carbonate and powdered steatile, or partially replacing carbon black. The modified fly ash is a renewable resource material with low cost and high quality.