Responsive chiral optical materials have gained considerable interests from the fields of sensing, display and optical devices. Materials that are capable of changing chiral optics under harsh conditions such as strong basic/acidic or ultra-high temperature provides thoughts for the design of materials working at special environments, which however, are still underdeveloped. Here, we report a proof-of-concept design of organogel that acts as matrices for thermal chiroptical switch with critical working temperature above 100°C. The reversible solution-to-gel transition of the specific β-cyclodextrin/dimethyl formide/LiCl system was initialized at about 130°C, when the luminophores with aggregation-induced-emission property shall be lighted up with transferred chirality from inherent chiral β-cyclodextrin. It allows for the controlled emergence of circularly polarized luminescence. This delicate design enables successful fabrication of ultra-high temperature thermal chiroptical switch. This article is protected by copyright. All rights reserved.