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A series of $${\left\hbox[ {{{\left\hbox( {{\rm{SnSe}}} \right\hbox)}_{1 \hbox+ \delta }}} \right\hbox]_m}{\left\hbox[ {{\rm{TiS}}{{\rm{e}}_2}} \right\hbox]_2}$$ heterostructure thin films built up from repeating units of m bilayers of SnSe and two layers of TiSe 2 were synthesized from designed precursors. The electronic structure of the films was investigated using X-ray photoelectron spectroscopy for samples with m = 1, 2, 3, and 7 and compared to binary samples of TiSe 2 and SnSe. The observed binding energies of core levels and valence bands of the heterostructures are largely independent of m . For the SnSe layers, we can observe a rigid band shift in the heterostructures compared to the binary, which can be explained by electron transfer from SnSe to TiSe 2 . The electronic structure of the TiSe 2 layers shows a more complicated behavior, as a small shift can be observed in the valence band and Se3 d spectra, but the Ti2 p core level remains at a constant energy. Complementary UV photoemission spectroscopy measurements confirm a charge transfer mechanism where the SnSe layers donate electrons into empty Ti3 d states at the Fermi energy.