A highly reflective counter electrode is prepared through the deposition of alternating layers of organized mesoporous TiO2 (om-TiO2) and colloidal SiO2 (col-SiO2) nanoparticles. We present the effects of introducing this counter electrode into dye-sensitized solar cells (DSSCs) for maximizing light harvesting properties. The om-TiO2 layers with a high refractive index are prepared by using an atomic transfer radical polymerization and a sol–gel process, in which a polyvinyl chloride-g-poly(oxyethylene) methacrylate graft copolymer is used as a structure-directing agent. The col-SiO2 layers with a low refractive index are prepared by spin-coating commercially available silica nanoparticles. The properties of the Bragg stack (BS)-functionalized counter electrode in DSSCs are analyzed by using a variety of techniques, including spectroscopic ellipsometry, SEM, UV/Vis spectroscopy, incident photon-to-electron conversion efficiency, electrochemical impedance spectroscopy, and intensity modulated photocurrent/voltage spectroscopy measurements, to understand the critical factors contributing to the cell performance. When incorporated into DSSCs that are used in conjunction with a polymerized ionic liquid as the solid electrolyte, the energy conversion efficiency of this solid-state DSSC (ssDSSC) approaches 6.6 %, which is one of the highest of the reported N719 dye-based ssDSSCs. Detailed optical and electrochemical analyses of the device performance show that this assembly yields enhanced light harvesting without the negative effects of charge recombination or electrolyte penetration, which thus, presents new possibilities for effective light management.