A new architecture for multifunctional photoelectrochemical devices, namely photovoltachromic devices, is disclosed here, capable of producing electric energy by solar conversion also modulating the devices' optical transmittance in a smart and aesthetically sounding fashion. These devices generally consist of a titanium dioxide photoelectrode and of a bifunctional patterned counter electrode made of platinum and amorphous tungsten oxide. The innovative configuration described hereafter proposes to split the single patterned counter electrode into two distinct electrodes, physically overlapped: the central one is suitably drilled in order to allow the electrolyte to fill both communicating chambers. These three electrode devices allow three independent operating modes: photovoltaic, photoelectrochromic, and photovoltachromic. In this paper, we report the optical, electrical, and electrochemical characterization of this innovative device, varying both available catalytic surface area and the type of sensitizing dye. We eventually obtained the following conversion efficiencies, 2.75%, 2.35%, and 1.91%, in samples having different catalytic areas (397, 360, and 320 mm(2), respectively). We inferred that the higher the platinum area on the interposed platinum-poly(ethylene naphthalate)-indium tin oxide counter electrode, the higher the photovoltaic conversion efficiency. On the other hand, a decrease of the intercommunication openings generates a slowdown of bleaching processes.