AbstractHerein, a library of trifluoroethyl substituted aminomaleimide derivatives are reported with small size and enhanced emissions in both solution and solid‐state. A diCH₂CF₃ substituted aminochloromaleimide exhibits the most efficient dual‐state emission (Φ_f >50 % in solution and solid‐state), with reduced quenching from protic solvents. This is attributed to the reduction of electron density on the maleimide ring and suppressed π‐π stacking in the solid‐state. This mechanism was explored in‐depth by crystallographic analysis, and modelling of the electronic distribution of HOMO‐LUMO isosurfaces and NCI plots. Hence, these dual‐state dyes overcome the limitations of single‐state luminescence and will serve as an important step forward for this rapidly developing nascent field.