The reaction between alcohols and Boc2O leads to the formation of tert-butyl ethers and/or Boc-alcohols, depending on the nature of the Lewis acid catalyst. Product distribution is mainly tuned by the anionic part of the salt. Perchlorates and triflates, anions with highly delocalized negative charge, give prevalent or exclusive ether formation. On the other hand, Boc alcohols are the main or exclusive products with un-delocalized isopropoxide or low-delocalized acetate ions. The metal ion influences only the reaction rate, roughly following standard parameters for calculating Lewis acidity. A reaction mechanism is supposed, and a series of experimental evidences is reported to support it. These studies allowed us to conclude that, to synthesize tert-butyl ethers, in reactions involving aliphatic alcohols, Mg(ClO4)2 or Al(ClO4)3 represents the best compromise between costs and efficiency of the reaction, while, in reactions involving phenols, Sc(OTf)3 is the best choice, since aromatic tert-butyl ethers are not stable in the presence of perchlorates.