Doping of bulk semiconductors has revealed widespread success in optoelectronic applications. In the past few decades, substantial effort has been engaged for doping at the nanoscale. Recently, doped colloidal quantum dots (CQDs) have been demonstrated to be promising materials for luminescent solar concentrators (LSCs) as they can be engineered for providing highly tunable and Stokes‐shifted emission in the solar spectrum. However, existing doped CQDs that are aimed for full solar spectrum LSCs suffer from moderately low quantum efficiency, intrinsically small absorption cross‐section, and gradually increasing absorption profiles coinciding with the emission spectrum, which together fundamentally limit their effective usage. Here, the authors show the first account of copper doping into atomically flat colloidal quantum wells (CQWs). In addition to Stokes‐shifted and tunable dopant‐induced photoluminescence emission, the copper doping into CQWs enables near‐unity quantum efficiencies (up to ≈97%), accompanied by substantially high absorption cross‐section and inherently step‐like absorption profile, compared to those of the doped CQDs. Based on these exceptional properties, the authors have demonstrated by both experimental analysis and numerical modeling that these newly synthesized doped CQWs are excellent candidates for LSCs. These findings may open new directions for deployment of doped CQWs in LSCs for advanced solar light harvesting technologies. Copper‐doped colloidal semiconductor quantum wells are successfully synthesized by nucleation doping technique. These newly synthesized doped nanoplatelets are successfully shown to be applied in luminescent solar concentrators thanks to their near‐unity photoluminescence quantum efficiencies (≈97%), profoundly step‐like absorption profiles, and higher absorption cross‐sections along with highly Stokes‐shifted tunable emission in visible‐to‐near‐infrared.