The chemistry of penta- and hexa-coordinated compounds continues to expand in its breadth and application. Regarding this, the synthesis, properties and structural investigations of novel cage-phosphoranes, spiro-phosphoranes, fluorophosphoranes and spiro-oxaphosphetanes have been briefly discussed. Pentacoordinated phosphoranes have also been postulated as intermediates in the synthesis of dibenzophospholes, the carbofluorination of alkynes, Wittig-type reactions and also organocatalytic Mitsunobu reactions. Moreover, studies of novel hexacoordinated fluorinated phosphorus(v) compounds have been also evaluated.