In this work, we demonstrate a new tapered prism-shaped luminescent solar concentrator (LSC), which guides most of the luminescence toward one edge instead of four, for the solar window application. Only one Si photovoltaic (PV) strip attached to the light-emitting sidewall is needed to collect the luminescence, which further reduces PV material cost and avoids electrical mismatch. To achieve high visible transmission and mitigate reabsorption, colloidal silicon quantum dots (SiQDs) with ultraviolet-selective absorption and large Stokes shift are used as the fluorophores. With the SiQD concentration equal to 8 mg mL−1, the SiQD-LSC as a solar window can attain a power conversion efficiency (PCE) equal to 0.27%, while ensuring high average visible transmission (AVT = 86%) and high color rendering index (CRI = 94 with AM1.5G as the incident spectrum). When adjusted to front-facing, the Si PV strip can harvest not only the direct sunlight but also the concentrated SiQD fluorescence guided from the LSC. As a result, the overall solar window PCE can be increased to 1.18%, and the PCE of the front-facing Si PV strip alone can be increased by 7% due to the luminescence guided from the SiQD-LSC.