Based on enantiopure S- or R-(1-phenylethylamino)methylphosphonic acid (pempH(2)), homochiral lanthanide phosphonates (S)-[Ln(pempH)(NO3)(2)(H2O)(2)] (S-Ln) and (R)-[Ln(pempH)(NO3)(2)(H2O)(2)] (R-Ln) (Ln = Eu, Tb, Ho) are obtained successfully. All six compounds are isostructural, showing chiral brick-wall-shaped layer structures. They are all optically active, exhibiting second harmonic generation responses 0.7 times that of urea. The Eu and Tb compounds display strong red and green luminescent properties, respectively, with long luminescent lifetimes at the level of milliseconds. The catalytic properties of the dehydrated S-Tb are studied.