Solar cells can be designed for indoor applications to provide a feasible solution for harnessing photon energy from indoor lighting. In this paper, we analyze the suitability of a selenium-based solar cell for gathering photon energy emitted by indoor light-emitting diodes (LEDs). The absorption band of selenium (Se) is found to be aligned with the LED spectrum, making it a promising contender for efficient indoor applications. In order to simulate the Se-based photovoltaic (PV) device, we started by calibrating the simulation model against a fabricated Se cell that was tested under AM1.5G. After the verification of the physical models and the technological key factors of the different layers incorporated in cell design, a systematic approach was performed to assess the operation of the Se solar cell under an LED light environment. We show an optimized power conversion efficiency (PCE) of 26.93% for the Se-based cell under LED illumination (311 μW/cm²). This is achieved by providing an effective design that incorporates a double-ETL structure, which can significantly improve the band alignment between the different layers of the cell device. The simulation results presented in this work serve to judge the potential of Se solar cells as indoor PVs and offer an approach for providing indoor use specifically designed for internet-of-things (IoT) devices.