We have developed a methodology for the synthesis of PAMAM-dendrimers and dendrons that allows synthesis of PAMAM-dendrimers carrying different wedges. This is expected to have huge impact on areas such as the biomedical applications of dendrimers, where the studies reported up to now either have been carried out with all-symmetrically functionalized compounds or with dendrimers that have been modified in a purely statistical manner. Access to precisely functionalized dendrimers opens completely new areas ranging from programmable self-assembly through systematic studies of structure-activity relations between PAMAM-dendrimers and biological systems to truly well-defined targeted drug delivery systems based on dendrimers.