Transition metal dichalcogenides (TMDC) are important representatives in the emerging field of two‐dimensional materials. At present their combination with molecular films is discussed as it enables the realization of van der Waals bound organic/inorganic hybrids which are of interest in future device architectures. Here, we discuss the potential use of molybdenum disulfide (MoS2) as supporting substrate for the growth of well‐defined, crystalline organic adlayers. By this means, hybrid systems between the TMDC surface and organic compounds can be prepared, allowing for the profound investigation of mutual optical and electronic coupling mechanisms. As model system, we choose pentacene and perfluoropentacene as prototypical organic semiconductors and analyze their film formation on MoS2(001) surfaces. In both cases, we observe smooth, crystalline film growth in lying molecular configuration, hence enabling the preparation of well‐defined hybrid systems. By contrast, on defective MoS2 surfaces both materials adopt an upright molecular orientation and exhibit distinctly different film morphologies. This emphasizes the importance of highly ordered TMDC surfaces with low defect density for the fabrication of well‐defined hybrid systems.

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