Introducing electronically active organic components into lower dimensional metal halide compounds is an effective strategy to improve the electronic properties of hybrid metal halide materials. We have previously used this strategy to explore hybrid halides with tetrathiafulvalenes (TTFs) and a series of lead iodides and bismuth halides were isolated. The electronic properties were improved notably using this modification. In this work, we expand the study of TTF based main-group metal halides to double metal halides with mixed lead and copper transition metals. Two hybrid TTF–lead–cuprous iodides, formulated as [TTF]₅[Pb₂Cu₂I₁₀]·H₂O (1) and [TTF]₂[PbCu₂I₆] (2), and two monometal analogues of [TTF]₂[Cu₄I₆]·H₂O (3) and [TTF]₂[Ag₄I₆] (4) were crystallographically characterized. The anion of 1 is a 0D cluster, while that of the others is a 1D chain structure. The anion structures of 1–4 are novel and are reported for the first time. The TTF moieties are stacked to form a 2D framework in 1 and 1D columns in 2–4. We found that the semiconductor properties of the hybrids are related to electron donation from an anion to a cation. The electronic state of the TTF cations is another significant factor that affects the electronic properties of the materials. More notably, this work proved that the conductivity and photoconductivity of the mixed metal iodides are superior to those of the monometal iodides.