Hybrid one-dimensional lead halides, containing the protonated 1,8-bis(dimethylamino)naphthalene moiety (C14H19N2, monoprotonated “proton sponge”), were prepared by simple one-pot methods and investigated in terms of crystal structure, morphology, thermal stability and electronic properties. The as-precipitated (C14H19N2)PbBr3 and (C14H19N2)PbI3 species are isostructural and crystallize in the orthorhombic Pbca space group, resulting in 1D crystal phases with ([PbX3]-) chains (built by face-sharing [PbX6] octahedra; X = Br, I), among which the (C14H19N2)+ cations are inserted. The two compounds display complete miscibility in the solid state: both (C14H19N2)PbI2Br and (C14H19N2)PbIBr2 crystal phases were successfully synthetized and do not show segregation effects. TGA and DSC measurements showed that, while all these materials are stable up to 250°C, the iodine-rich (C14H19N2)PbI3 …