Two new organically templated lead(ii) iodide complexes, [(nbq)(PbI₃)]_n 1 and {[(CH₃)₃NC₂H₄N(CH₃)₃]₃(Pb₆I₁₈)}_n 2, have been synthesized in the presence of aromatic and aliphatic quaternary ammonium compounds, N-(n-butyl)quinolinium (nbq⁺) and [(CH₃)₃NC₂H₄N(CH₃)₃]²⁺, respectively, acting as structure-directing agents. Both 1 and 2 consist of uncoordinated structure-directing agents and inorganic moieties bound to the organic structure-directing agents. In 1, an inorganic (PbI₃^–)_n one-dimensional polyanion chain is built up by face-sharing of distorted PbI₆ tetrahedra. The inorganic framework of 2 presents a two-dimensional arrangement that could be discussed in terms of [Pb₃I₁₀]^4– building blocks. Static attractive interactions between organic countercations and inorganic moieties were revealed through the crystal packing. Density functional theory calculations indicate that 1 possesses semiconductor properties, tuned by the π-electrons of nbq⁺. In contrast, 2 is conductive in the direction of aliphatic quaternary ammonium moiety.