The fluorescent modes and signs of the circularly polarized luminescence of an axially chiral binaphthyl-pyrene organic fluorophore were successfully controlled by changing from a fluidic chloroform solution to a glassy poly(methyl methacrylate) solid film.

The signs of solid‐state circularly polarized luminescence (CPL) of axially chiral binaphthyl organic fluorophores were successfully controlled by changing the environment of their solid‐state matrices from a poly(methyl methacrylate) (PMMA) film‐dispersed state to a KBr pellet‐dispersed state.

2,2-Dimethyl-1,3-dioxolane connected to two pyrene moieties through flexible wires in chloroform exhibited cryptochirality in the ground state, as proven by the lack of detectable circular dichroism signals. This cryptochirality was deciphered in the photoexcited state by circularly polarised luminescence signals.

Tethering four 1- versus 2-naphthyls to the same chiral scaffold derived from tartaric acid led to oppositely signed circularly polarized luminescence (CPL) and circular dichroism (CD) in solution, which not only reveals the decisive role of the spatial arrangement of chromophores/fluorophores in determining the chiroptical behaviors but also provides us with a versatile tool for switching the signs of CPL and CD without using the antipodal scaffold.