The invention belongs to the field of water treatment, and discloses a modified composite adsorbent as well as a preparation method and application thereof. The preparation method of the modified composite adsorbent comprises the following steps: adding an aluminum salt aqueous solution into an alkaline solution under stirring until the pH value of an obtained solution is 6.5-7.5, heating an obtained suspension in a sealed manner, filtering, washing, drying and heating to obtain aluminum oxide; adding aluminum oxide in an acetic acid solution of chitosan, adding glutaraldehyde to form a colloid, drying, grinding, washing, drying, adding an obtained chitosan composite aluminum oxide into deionized water, adding a cationic surfactant, stirring, filtering, washing with ethanol and deionizedwater, and drying to obtain a finished product. The preparation method of the modified composite adsorbent is simple, and the adsorbent has the advantages of strong adsorption capacity, high adsorption efficiency on ionic dyes, easiness in separation from a reaction solution, no secondary pollution to the environment and the like, can effectively adsorb the ionic dyes in printing and dyeing wastewater, and is suitable for treating the printing and dyeing wastewater containing the ionic dyes.