Luminescence of ferroelectric materials is one important property for technological applications, such as low-energy electron excitation. However, the vast majority of doped inorganic ferroelectric materials have low luminescent efficiency. The past decade has envisaged much progress in the design of both ferroelectric and luminescent organic–inorganic hybrid complexes for optoelectronic applications. The combination of ferroelectricity and luminescence within organic–inorganic hybrids would lead to a new type of luminescent ferroelectric multifunctional materials. We herein report a hybrid molecular ferroelectric, (pyrrolidinium)­MnCl3, which exhibits excellent ferroelectricity with a saturation polarization of 5.5 μC/cm2 as well as intense red luminescence with high quantum yield of 56% under a UV excitation. This finding may extend the application of organic–inorganic hybrid compounds to the field of ferroelectric luminescence and/or multifunctional devices.