The reaction of POCl 3 with the trinuclear bisphenol 1 has been investigated. All three homeomorphic in,out-isomers of the phosphorus cryptand were isolated. Among them the out,out-isomer was the main macrobicyclic product obtained. The reaction of the previously described in,in-phosphite 2 with CuCl afforded an interesting complex containing two metal centers bridging the cavity of the cryptand together with a central chloride ion. This complex suggested the use of Cu(I) as a template for the formation of the formerly described in,outphosphite cryptands. With this method it is now possible to carry out the reaction in higher concentrated solution to isolate larger quantities of the phosphorus macrobicycles.