been made by introducing disorder in the systems via alloying, complex crystal-engineering, [4,5] and by creating interfaces in thin films. [2] Hicks and Dresselhaus originally proposed that quantum well structures should be capable of lowering the thermal conductivity with only a minor impact on the electrical conductivity; [6] note that the latter point is particularly important for the application in thermoelectrics. Experimentally the phenomenon has been demonstrated, e.g., by Hicks et al. [7] in the PbTe/(Pb,Eu)Te system and by Ohta et al. [8] in the SrTiO 3 /Sr(Ti,Nb)O 3 system. Layered structures that show reduced thermal conductivity have been reported for a number of other material systems as well, such as CaTiO 3 /SrTiO 3 , [9] W/ Al 2 O 3 , [10] PbTe/PbSe, [11] IrSb 3 /CoSb 3 , [12] AlN/GaN, [13] TiNiSn/ HfNiSn, [14] Si/Ge (including alloy variants), [15][16][17][18][19] GaAs/AlAs (including alloy variants), [20][21][22][23] Bi 2 Te 3 /Sb 2 Te 3 , [24] InAs/AlSb, [25] InGaAs/InGaAsP, [26] and Ge 2 Te 3 /Sb 2 Te 3 , [27] to name a few. Most such inorganic-inorganic interfaces utilize isoelectronic substitution to retain the electrical conductivity and the high degree of crystallinity of the samples, which essentially grow epitaxially. An exception are the crystalline-amorphous interfaces as reported, e.g., in the Al 2 O 3 /TiO 2 [28] and Si [29] systems. With regard to high-quality interfaces, inorganic-organic superlattices offer an attractive option to reduce thermal conductivity compared to a homogeneous inorganic thin film. Owing to the large acoustic impedances between the inorganic and organic materials, we may anticipate considerably lowered thermal boundary conductance across the inorganic-organic interface. [30] Remarkable results have been reported for, e.g., TiS 2 with organic molecules intercalated either electrochemically [31] or chemically [32] from an organic solution. We have, on the other hand, fabricated ZnO/benzene [33,34] and TiO 2 /benzene [35,36] superlattices using the gas-phase atomic/molecular layer deposition (ALD/MLD) thin-film technique to demonstrate reductions in thermal conductivity of several orders of magnitude. Among the benefits of the ALD/MLD technique over solution-based intercalation routes is that it allows the precise control of the introduction frequency of the organic layers within the inorganic matrix.The uniting concept to lower the thermal conductivity of superlattice and nanolaminate structures is to suppress phonon Nanoscale superlattice structures are known to significantly suppress the thermal conductivity in thin films due to phonon scattering at the interfaces of the mutually different layers. Here it is demonstrated that in addition to the number of interfaces, their spacing within the film can lead to a reduction in thermal conductivity. The proof-of-concept data are for ZnO/benzene thin films fabricated through sequential gas-surface reactions in atomic/ molecular layer precision using the atomic/molecular layer deposition technique. In comparison to...