The invention discloses a preparation method of composite special paper with high electrical conductivity. The preparation method comprises the following steps: using polyvinyl alcohol as a matrix, and organically modifying a polyvinyl alcohol molecule by using an epoxy monomer and a titanate coupling agent through a nucleophilic substitution reaction mechanism or a chemical graft modification method to obtain modified polyvinyl alcohol dispersion liquid; then using an aniline monomer as a raw material, adopting protonic acid or organic acid for doping, using persulfide as an oxidant, and enabling the aniline monomer to be subjected to graft polymerization on the surface of the modified polyvinyl alcohol by adopting a graft polymerization method to obtain water-based polyaniline grafted and modified polyvinyl alcohol composite conductive dispersion liquid; using the water-based polyaniline grafted and modified polyvinyl alcohol composite conductive dispersion liquid as a surface coating agent and coating on the paper surface, thereby obtaining the composite special paper with the high electrical conductivity. In the whole preparation process, water is adopted as a solvent and no organic solvent is added, so the composite special paper is economical and environment-friendly. The composite special paper with the high electrical conductivity, disclosed by the invention, has excellent electrical conductivity, conductive stability and mechanical properties and can be applied to the fields of static electricity resistance, electromagnetic shielding and the like.