Superlattice materials offer new opportunities to modify optical and electrical properties of recently emerging 2D materials. The insertion of tetraethylbenzidine (EtDAB) into interlamination of the established 2D PbI2 semiconductor through a mild solution method yielded the first lead iodide superlattice, EtDAB⋅4PbI2 (EtDAB=tetraethylbenzidine), with radical and non‐radical forms. The non‐radical form has a non‐ionic structure that differs from the common ionic structures for inorganic–organic hybrid lead halides. The radical form shows five orders of magnitude greater conductance and broader photoconductive response range (UV/Vis → UV/Vis‐IR), than pure PbI2 and the non‐radical form of the superlattice. Lead the way: The first lead‐iodide superlattice constructed from non‐ionic organic molecules and PbI2 through van der Waals interactions is a new type of inorganic–organic hybrid and has a radical and a non‐radical form. The radical form has an almost five orders of magnitude greater conductivity and broader band photoconductive response than that of the non‐radical form or pure PbI2.