Passing from fossil energy sources to renewable ones, meanwhile answering the increasing world energy demand, will require innovative and low-cost technologies. Smart photovoltaic windows could fulfill our needs in this matter. Their transparency can be controlled to manage solar energy and regulate interior temperature and illumination. Here, we present the one-pot synthesis of polymer-dispersed liquid crystals (PDLCs), in which highly red-NIR phosphorescent transition metal clusters are selectively embedded, either in the polymer, in the liquid crystal, or in both phases. The PDLC matrix is used as a tunable waveguide to transfer the emitted light from nanoclusters to the edge of the device, where solar cells could be placed to convert it into electricity. Edge emission is obtained in both "off" and "on" states, with a maximum intensity for the scattering "off" one. These doped PDLCs showing photo-activity features and high stability under voltage represent key stepping stones for integration in buildings, displays, and many other technologies.