A versatile new concept is presented for the synthesis of Janus colloids composed of Laponite nanoclay armored poly(divinylbenzene) with an anisotropic surface potential via a double Pickering emulsion template. First, polystyrene or poly(divinylbenzene) colloids stabilized with Laponite nanoclay are synthesized via a Pickering miniemulsion approach. These nanoparticle-stabilized colloids were then templated at a wax-water interface in a second Pickering emulsion in order to chemically modify one hemisphere of the colloids. Janus modification of the colloids was accomplished by cation exchange of sodium ions, originally present on the surface of the Laponite with various salts of modifying ions (Ca(2+), Fe(2+), and Fe(3+)) in the suspension. The zeta potential of the chemically modified and unmodified colloids was compared. The maximum change in the zeta potential was given by the calcium ions, Ca(2+)-adsorbed modified colloids as compared to unmodified sodium ions, Na(+)-adsorbed colloids. The distribution of charges on the Janus colloids results in a nonuniform zeta potential. XPS and optical microscopy were used to verify the successful chemical modification by the cation exchange of Na(+) for Ca(2+) ions on one hemisphere of the Janus colloids.