Reductive coupling of aromatic carbonyl compounds in the presence of stoichiometric amounts of Sm(II) compounds such as SmI2, SmI2/TMSiCl, SmBr2, Sm/TMSiBr, SmCp2 resulted in hydrobenzoin derivatives. OH‐functionalized poly(p‐xylylene)s (OH‐PPX) were obtained by reductive coupling of aromatic dialdehydes. The usage of solubilizing groups as well as the use of trimethylsilylchloride (TMSiCl) and trimethylsilylbromide (TMSiBr) enhanced the polymerizability of monomers under study. In spite of moderate yields high molecular weight polymers were obtained.