Multilayers consisting of polypyrrole/poly(styrene sulfonate) (PP/PSS) and polyviologen (PV) were electrochemically prepared on Au to enhance long-term and environmental (e.g., pH) stability of PV modified electrodes. PV cationic polyelectrolytes were adsorbed on top of electrochemically synthesized PP/PSS via electrostatic interactions with PSS present at the surface of conducting polymer substrates. By alternating electrochemical synthesis of PP/PSS and PV adsorption in a single medium, multilayers were prepared up to 13 layer-pairs. The electrochemical and electrochromic properties of multilayers produced in this way were quite reproducible, since the film preparation does not require medium changes and the layer thicknesses can be finely controlled using the applied potential and time. Although the redox potential of PP/PSS shifted in the positive direction with increase in the number of layer-pairs, cyclic voltammograms of multilayers indicated that total electroactivity of PP/PSS was retained. PV molecules, sandwiched between reduced PP/PSS layers, were also fully electroactive and quite stable during repeated redox switching processes, indicative of enhanced long-term stability. Multilayers also possessed electrochromic properties which were directly proportional to the number of PV layers.