Three new hydrogen bonding motifs of phosphine oxides involving a silanol, a phenol, and chloroform are described. The single crystal X-ray structures, in combination with the NMR and IR data of the new adducts Ph3PO center dot HOSiPh2OSiPh2OH center dot OPPh3, which features a linear Si-O-Si linkage, Cy3PO center dot HO(2,6-Bu-t(2)-4-Me(C6H2), and Cy3PO center dot HCCl3, are reported and discussed.