A new synthetic approach leading to asymmetrically substituted polyphenylene dendrimers is presented. Following this method, polyphenylene dendrimers decorated with an increasing number of chromophores at the periphery have been obtained up to the second generation. Especially the synthesis of a polyphenylene dendrimer beating three donor chromophores and one acceptor chromophore has been realized. Intramolecular energy transfer within this molecule is demonstrated by applying absorption and fluorescence measurements.