Polypyrrole/polyester-cotton composites were prepared using pyrrole as the monomer, adopting an in situ polymerization on the plain polyester-cotton fabric. The influence of the pyrrole concentration, type and concentration of doping agents on the dielectric properties and conductivity of polypyrrole/polyester-cotton composites were investigated using the method of control variables. The results show that within the frequency range 0.01–1.0 GHz, and for concentrations of pyrrole monomers of 0.3, 0.6, 0.9, 1.2 and 1.5 mol/L, the polypyrrole/polyester-cotton composite had the strongest polarization ability, dissipation ability and absorbing-attenuation ability to electromagnetic waves, and the surface resistance was the smallest and conductivity was the best when the pyrrole concentration was 0.9 mol/L. Within the same frequency range, five doping agents were tested, namely sodium dodecyl benzene sulfonate, p-toluenesulfonic acid, ferric chloride, sodium lignosulfonate and camphor sulfonic acid. The composite with sodium dodecyl benzene sulfonate as the doping agent had the strongest polarization ability, dissipation ability and absorbing-attenuation ability to electromagnetic waves, the lowest surface resistance and the strongest conductivity. Finally, within the same frequency range and using doping agent concentrations of 0.1 and 0.2 mol/L, the composite with doping agent concentration of 0.1 mol/L had the strongest polarization ability, dissipation ability and absorbing-attenuation ability.