A new chiral cerium halide, R/S-MCC, has been synthesized for the first time, exhibiting circularly polarized luminescence (CPL) in the ultraviolet (UV) region. This is the first chiral rare-earth (RE) based organic-inorganic hybrid metal halide (OIHMH) with UV CPL. The chiral properties are transferred from the chiral organic cations to the inorganic cerium chloride framework. The emission spectra of R/S-MCC are in the UV region, originating from the d-f transition of Ce³⁺, making them ideal candidates for UV CPL light sources. R- and S-MCC are the first RE-based OIHMHs and the first chiral metal-halides with UV CPL. The unique optical, electrical, magnetic, and spintronic properties of RE elements combined with chirality could accelerate the development of chiral optoelectronics and spintronics. The single crystals of R/S-MCC were synthesized via a solution method and grown by an antisolvent-assisted crystallization strategy. Single-crystal X-ray diffraction revealed that R-MCC and S-MCC belong to the triclinic crystal system and crystallize into the asymmetric Sohncke space group of P1. The crystal structures of R/S-MCC are mirror symmetric, and each Ce³⁺ coordinates with six chloride ions and two methanol molecules, forming a distorted dodecahedron. The chirality transfer is further supported by the crystallographic indexing based on Wilson statistics and the cumulative intensity distribution, which match well with the acentric curve. The ⟨|E²-1|⟩ value is 0.763 for both R- and S-MCC, suggesting their space groups are non-centrosymmetric. This work opens a new avenue for the development of chiral OIHMHs towards RE-based chiral OIHMHs.A new chiral cerium halide, R/S-MCC, has been synthesized for the first time, exhibiting circularly polarized luminescence (CPL) in the ultraviolet (UV) region. This is the first chiral rare-earth (RE) based organic-inorganic hybrid metal halide (OIHMH) with UV CPL. The chiral properties are transferred from the chiral organic cations to the inorganic cerium chloride framework. The emission spectra of R/S-MCC are in the UV region, originating from the d-f transition of Ce³⁺, making them ideal candidates for UV CPL light sources. R- and S-MCC are the first RE-based OIHMHs and the first chiral metal-halides with UV CPL. The unique optical, electrical, magnetic, and spintronic properties of RE elements combined with chirality could accelerate the development of chiral optoelectronics and spintronics. The single crystals of R/S-MCC were synthesized via a solution method and grown by an antisolvent-assisted crystallization strategy. Single-crystal X-ray diffraction revealed that R-MCC and S-MCC belong to the triclinic crystal system and crystallize into the asymmetric Sohncke space group of P1. The crystal structures of R/S-MCC are mirror symmetric, and each Ce³⁺ coordinates with six chloride ions and two methanol molecules, forming a distorted dodecahedron. The chirality transfer is further supported by the crystallographic indexing based on Wilson statistics and the cumulative intensity distribution, which match well with the acentric curve. The ⟨|E²-1|⟩ value is 0.763 for both R- and S-MCC, suggesting their space groups are non-centrosymmetric. This work opens a new avenue for the development of chiral OIHMHs towards RE-based chiral OIHMHs.