Electroactive thin films are an important element in the devices devoted to energy conversion, actuators, and molecular electronics, among others. Their build-up by the layer-by-layer technique is an attractive choice since a fine control over the thickness and composition can be achieved. However, most of the assemblies described in the literature show a lack of internal order, and their thicknesses change upon oxidation-state alterations. In this work, we describe the formation of layer-by-layer assemblies of redox surfactants and polyelectrolytes that leads to the construction of mesoscale organized electroactive films. In contrast to thin films prepared with traditional redox polymers, here, the redox surfactant does not only allow the control of the film meso-organization (from 2D hexagonal to circular hexagonal phases) but it also allows the control of the number and position of the redox centers. Finally, these films show high stability and a negligible structural deformation under redox-state changes.