Subsequent to our previous studies on the SET formation mechanism on the single crystal silicon (100) surface, here we report on complementary studies of the SET formation on Si surfaces with the crystal orientations (111) and (110). The differences in electrochemical behavior of the different crystal orientations are discussed - especially with regard to the effect of the SET forming electrolyte additives fluoroethylene carbonate (FEC) and vinylene carbonate (VC) added to ethylene carbonate (EC)/diethyl carbonate (DEC) based electrolytes. Fourier transform infrared spectroscopy (FUR) of the SET during early stages of SET formation and physico-chemical investigations (wetting behavior) indicate a strong dependence of the chemical composition of the SET on the surface orientation and the electrolyte composition during the early stages of lithiation of Si. However, at a higher lithiation degree less difference in the chemical composition of the SET can be observed. These findings are in agreement with those made for the SEI formation on the Si(100) surface.