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The electronic properties and growth morphology of Si(111)/ZnS heterostructure modified by a GaSe van der Waals termination layer, which provides a chemical and an electronic passivation of the Si(111)‐surface is investigated by surface sensitive methods (STM, LEED and SXPS). The van der Waals termination layer suppresses the Si‐S interface reaction, which is observed for non terminated substrates. The interface electronic properties are nearly unchanged, but the morphology of the growing ZnS‐film is dramatically changed. With the passivation layer ZnS grows as orientated pyramides with a (111) base area surface orientaion and (100)‐facets. The sticking coefficient is reduced by a factor of ≈10 compared to bare Si(111), where ZnS grows as an untextured polycrystalline layer.