A　series　of　multinuclear　lanthanide-covalent　organic　polyhedra　(LnCOPs),　including　pillar-typed　triangular　prisms　1-Ln(3)　and　tetrahedra　2-Ln(4)　(Ln　=　La-III,　Sm-III,　Eu-III),　have　been　constructed　for　the　first　time,　through　either　one-pot　subcomponent　self-assembly　or　postassembly　metalation.　In　contrast　to　the　known　tetrahedral　cages　based　on　transition　metals,　the　pillar-typed　polyhedra　were　favored　from　the　same　organic　components　in　the　presence　of　lanthanides.　Besides　this,　facile　transmetalations　between　the　1-Ln(3)　polyhedra　endow　cascade　chameleonic　luminescence.　Meanwhile,　the　open　metal　sites　and　pendent　amine　groups　on　1-Ln(3)　enable　these　polyhedra　to　catalyze　the　Henry　reaction　efficiently.