Intelligent multifunctional materials are indispensable for the electronic devices, but the existing applied counterparts have the disadvantage that their structures cannot be adjusted to meet diversified application requirements. Therefore, organic-inorganic hybrid perovskites with the inherent advantage of structural diversity are expected to become promising intelligent multifunctional materials. Based on the diversity of perovskites mentioned above, we have reported a series of dielectric switches. Here, a new one-dimensional organic-inorganic hybrid perovskite (N-fluoroethyl-N-methylmorpholine)PbBr3 was reported. In this distorted octahedral perovskite, a step-like dielectric switching was observed at around 343 K upon heating and 325 K upon cooling. Simultaneously, photoluminescence is also related to the highly distorted octahedron, and this one-dimensional Pb-based halide exhibits a red-light with CIE chromaticity coordinates of (0.56, 0.42) upon ultraviolet photoexcitation. In short, the reversible/switchable dielectric phase transition and photoluminescence characteristic in this hybrid perovskite was successfully achieved, which are expected to be applied in optoelectronic devices and dielectric switches, and promote the development of organic-inorganic hybrid multifunctional materials.