The convergent synthesis of novel dendrimeric systems containing NLO-ligands is described. The poor solubility properties of dendrimers of type A containing NLO-ligands enticed us into developing novel dendrimers of type B leading to the convergent synthesis of third generation NLO-containing dendrimer 15 containing branches of unequal length. Furthermore, a strategy was developed for connection of dendrons leading to dendrimer-to-dendrimer systems of type C. For this a dendrimer was required of which selectively one branch could be deprotected i.e. dendrimer 22. To the deprotected branch a next dendrimer moiety was attached leading to 23, also containing a deprotectable branch, which was used for attachment of another dendrimer moiety, leading to dendrimer-to-dendrimer system 24.