We report the preparation of hollow spherical polypyrrole balls (HSPBs) by two different approaches. In the first approach, core-shell conductive balls, CSCBs, were prepared with poly(styrene) as core and polypyrrole (PPy) as shell by in situ polymerization of pyrrole in the presence of polystyrene (PS) latex particles. In the other approach, CSCBs were obtained by in situ copolymerization of pyrrole in the presence of PS(F) with hydrophilic groups like anhydride, boronic acid, carboxylic acid, or sulfonic acid, and then HSPBs were obtained by the removal of PS or PS(F) core from CSCBs. TEM images reveal the spherical morphology for HSPBs prepared from PS(F). The conductivity of CSCBs and HSPBs was in the range of 0.20–0.90 S/cm2.