Molecular ferroelectrics have attracted considerable interests because of their easy and environmentally friendly processing, low acoustical impedance and mechanical flexibility. Herein, a molecular thermochromic ferroelectric, N,N′‐dimethyl‐1,4‐diazoniabicyclo2.2.2octonium tetrachlorocuprate(II) (DMe‐DABCOCuCl4) is reported, which shows both excellent ferroelectricity and intriguing thermochromism. DMe‐DABCOCuCl4 undergoes a ferroelectric phase transition from Pca21 to Pbcm at a significantly high Curie temperature of 413 K, accompanied by a color change from yellow to red that is due to the remarkable deformation of CuCl42− tetrahedron, where the ferroelectric and paraelectric phases correspond to yellow and red, respectively. Combined with multiple bistable physical properties, DMe‐DABCOCuCl4 would be a promising candidate for next‐generation smart devices, and should inspire further exploration of multifunctional molecular ferroelectrics. Set phases to stun: A molecular thermochromic ferroelectric, N,N′‐dimethyl‐1,4‐diazoniabicyclo2.2.2octonium tetrachlorocuprate(II), undergoes a ferroelectric phase transition from Pca21 to Pbcm at the significantly high Curie temperature (Tc) of 413 K. This is accompanied by a color change from yellow to red that is due to the remarkable deformation of the CuCl42− tetrahedron.