Organic−inorganic hybrid materials are highly versatile and can be easily modified, allowing for the deliberate construction of multifunctional ferroelectrics. In particular, the combination of photoluminescence and ferroelectricity in a single hybrid material holds great potential for various applications, such as lighting sensors, memory devices, and other multifunctional uses. In this study, we focused on 3-oxa-8-azabicyclo[3.2.1]octane hydrochloride (OAO) and designed two room-temperature ferroelectrics based on manganese (Mn):Both of these compounds crystallize in the polar orthogonal space group Pna2 1 , displaying robust photoluminescence and ferroelectricity at room temperature. The saturation polarizations of OAO-MnCl 4 and OAO-MnBr 4 are approximately 0.51 and 0.59 μC/cm 2 , respectively. Interestingly, the single crystal of OAO-MnCl 4 demonstrates dual-emission bands at 550 and 670 nm, which are attributed to self-trapped excitons. Additionally, OAO-MnCl 4 exhibits a reversible thermochromic phenomenon, displaying sensitive luminescent switching between green and red emissions within a narrow temperature range. This room-temperature molecular ferroelectric with photoluminescence opens up new avenues for designing novel multifunctional ferroelectrics and establishes a foundation for potential optoelectronic applications of these luminescent Mn-based materials.