A novel method of creating ultrathin, well‐ordered organic multilayer films is described, in which freely suspended smectic liquid crystal films are transferred to solid substrates. X‐ray and optical measurements show that both the smectic layering and the in‐plane director field, which are the defining characteristic structures of the original free film, are maintained after transfer. This method, in contrast to traditional techniques of organic film deposition, offers the possibility of orienting the initial freely suspended liquid crystal films using applied fields to obtain highly organized monodomain structures after transfer.