In the realm of molecular phase transition research, particularly for applications in sensors, data storage and switching technologies, the role of organic-inorganic hybrid perovskite materials has been increasingly recognized for their significant potential. Nevertheless, hybrid post-perovskites, as a critical subclass of perovskites, have not been thoroughly studied and mainly limit in the instances based on polyatomic bridging agents like dicyanamide (dca⁻) and non-cyclic organic cations. Herein, a polar cyclic quaternary ammonium cation, N,N-dimethylpyrrolidinium (DMP⁺), was used to assemble a new hybrid post-perovskite, (DMP)[Mn(dca)₃] (1), which undergoes a phase transition from orthorhombic Bmmb to monoclinic P2₁/n space group at 249 K. By employing multiple techniques such as differential scanning calorimetry, variable-temperature single-crystal X-ray analysis, dielectric measurements, and Hirshfeld surface analysis, we disclosed the role of polar cyclic quaternary ammonium DMP⁺ in elevating the phase-transition temperature by 48 K, generating significant dielectric switching effect and facilitating interlayer sliding of inorganic framework.