2D halide perovskite-like semiconductors are attractive materials for various optoelectronic applications, from photovoltaics to lasing. To date, the most studied families of such low-dimensional halide perovskite-like compounds are Ruddlesden–Popper, Dion–Jacobson, and other phases that can be derived from 3D halide perovskites by slicing along different crystallographic directions, which leads to the spatially isotropic corner-sharing connectivity type of metal-halide octahedra in the 2D layer plane. In this work, a new family of hybrid organic–inorganic 2D lead halides is introduced, by reporting the first example of the hybrid organic–inorganic post-perovskite 3-cyanopyridinium lead tribromide (3cp)PbBr₃. The post-perovskite structure has unique octahedra connectivity type in the layer plane: a typical “perovskite-like” corner-sharing connectivity pattern in one direction, and the rare edge-sharing connectivity pattern in the other. Such connectivity leads to significant anisotropy in the material properties within the inorganic layer plane. Moreover, the dense organic cation packing results in the formation of 1D fully organic bands in the electronic structure, offering the prospects of the involvement of the organic subsystem into material's optoelectronic properties. The (3cp)PbBr₃ clearly shows the 2D quantum size effect with a bandgap around 3.2 eV and typical broadband self-trapped excitonic photoluminescence at temperatures below 200 K.