Luminescent solar concentrators (LSCs) are devices that can collect sunlight from a large area, concentrating it at the borders of the slab, to achieve efficient photovoltaic conversion when small area solar cells are placed at their edges, realizing building-integrated photovoltaics. Efficient luminophores in terms of high luminescence quantum yield are needed to obtain high-performance LSCs. A key point is the ability to engineer the Stokes shift (i.e. the difference between the maximum of the absorption and emission spectra), to minimize reabsorption processes. In this work, we report novel silicon-doped carbon nanodots (Si-CDs) with an ultrahigh quantum yield (QY) up to 92.3% by a simple hydrothermal method. Thin-film structured LSCs (5 × 5 × 0.2 cm3) with different concentrations of Si-CDs are prepared by dispersing the Si-CDs into polyvinyl pyrrolidone (PVP) matrix, and the optimal power conversion efficiency (PCE) of LSCs can be as high as 4.36%, which is nearly 2.5 times higher than that prepared with silicon-undoped CDs. This Si-CDs/PVP film LSC has a high QY of 80.5%. A large-area LSC (15 × 15 cm2) is also successfully fabricated, which possesses a PCE of 2.06% under natural sunlight irradiation (35 mW·cm-2), one of the best reported values for similar size LSCs. The efficient Si-CDs as luminescent substances for high-efficiency large-area LSCs will further give an impetus to the practical exploitation of LSCs.