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Single-crystal structures of five lanthanide-erythritol complexes are reported. The analysis of the chemical compositions and scrutinization of structural features in the single-crystal data of the complexes led us to find that unexpected deprotonation occurs on the OH group of erythritol of three complexes. Considering these complexes were prepared in acidic environments, where spontaneous ionization on an OH group is suppressed, we suggest metal ions play an important role in promoting the proton transfer. To find out why the chemical