In most chiral organic–inorganic hybrid metal halides, chirality is extrinsically introduced by chiral organic cations because the inorganic framework is otherwise achiral. However, there are a few hybrid metal halides where chirality emerges spontaneously, i.e. in the absence of chiral molecules. Yet, the mechanisms that cause this intrinsic chirality to emerge are unclear. In this work, we report the discovery and investigation of the intrinsically chiral material pyrrolidinium palladium chloride ((C₄H₁₀N)PdCl₃), which consists of bent edge-sharing square-planar palladium chloride dimers separated by [C₄H₁₀N]⁺ cations. Its crystal structure indicates that hydrogen bonding interactions between N-bound hydrogens and Cl⁻ anions induce chirality, and this hypothesis is supported by the achirality of the all-inorganic material CsPdCl₃ as well as our density functional theory calculations. The situation is reversed for octahedrally coordinated copper(II) chlorides, where previous reports show that (C₄H₁₀N)CuCl₃ is achiral while CsCuCl₃ exhibits intrinsic chirality. This reversal is caused by the electronic degeneracy in octahedral Cu²⁺. In CsCuCl₃, cooperative Jahn–Teller distortions cause Cu²⁺ ions to move off-center within their octahedra, inducing chirality, while hydrogen bonding interactions with (C₄H₁₀N)CuCl₃ break symmetry, so the cooperative chiral distortion no longer occurs. Although the source of intrinsic chirality is usually unclear, our findings show that hydrogen bonding interactions can cause intrinsic chirality to emerge in organic–inorganic hybrid materials. They also highlight the importance of the metal's electron configuration and metal-halide coordination geometry on the emergence of intrinsic chirality, thereby providing guidance for the targeted synthesis of intrinsically chiral organic–inorganic hybrid materials.