<p>Luminescent solar concentrators (LSCs) offer a sustainable approach to power generation using fluorescent glasses, yet their green industrialization is impeded by the limited production scale and non-recyclability of embedded nanocrystals. Here, we introduce a lead-free perovskite derivative ETP₂SbCl₅ (ETP = (C₆H₅)₃PC₂H₅) with a reversible transition between powder and glass states. Through molecular dynamics and density functional theory, we elucidate the possible structural distortions of [SbCl₅] pyramids and their impact on luminescence. The fabricated LSCs, utilizing such fluorescent glasses with an efficient absorption for &lt;420 nm, achieve the highest power conversion and optical efficiencies of ~5.56% and ~32.5%, respectively. In addition to self-healing by reheating at ~200 °C, impressively, it could be mass recycled to phosphor by ethanol or heating treatments, which still maintains nearly initial fluorescent performance and could be repurposed like freshly synthesized samples. This work presents a paradigm for the sustainable use of fluorescent materials and offers a reliable path toward low-carbon globalization.</p>