The invention discloses a composite fluorine removal agent. The composite fluorine removal agent is formed by porous coal in a multi-layer hole diameter structure and active fluorine removal particles embedded in the porous coal. The active fluorine removal particles are produced by natural minerals containing Al or Mg through crushing and high-temperature activating in porous coal diameters. The active fluorine removal particles and the porous coal are firmly integrated and scattered uniformly. A preparation method comprises the steps of natural mineral crushing screening, composite fluorine removal agent precursor matching and activating, pore forming material removal and the like. According to the composite fluorine removal agent and the preparation method, the method is simple, the operation is facilitated, the prepared composite fluorine removal agent is used for removing fluorine in zinc sulfate leach liquor during zinc removal hydrometallurgy and has the advantages of being large in fluorine removal amount and rapid and efficient, the composite fluorine removal agent can be recycled through regeneration of inorganic aluminum salt, inorganic magnesium salt or alkali liquor easily, and the fluorine removal comprehensive cost is low.