Members of a new family of chiral triskelion P ligands, namely helical C-3-symmetric monophosphites P(OR)(3), have been prepared in two steps by monoacylation of (R)- or (S)-1,1'-binaphthyl-2,2'-diol (BINOL) or diphenol using a carboxylic acid chloride followed by PCl3 phosphorylation. The most sterically hindered member of these monophosphites, derived from the compound accessible by monoacylation of BINOL using adamantane carboxylic acid chloride, has been characterized by X-ray crystallography and NMR spectroscopy as a single well-defined compound. It exists exclusively in the syn conformation, with a propeller-like (twisted) geometry resulting in helicity. Upon utilization of (R)- or (S)-BINOL in the two-step synthesis, the helicity proves to be P or M, respectively. When used as ligands in the Rh-catalyzed asymmetric hydrogenation of prochiral homoallylic alcohols, these bulky helical ligands lead to respectable enantioselectivities (79-98% ee). In contrast, the less sterically congested and more flexible BINOL-derived phenyl analogue exists in several conformeric forms, even in the crystal, and this leads to poor enantioselectivity in the model reactions (ee = 32%). For the purpose of structural comparison, the analogous monophosphites derived from diphenol were also prepared and characterized. These compounds, again in contrast to the BINOL-derived adamantyl derivatives, occur in several different conformeric states.