The efficient synthesis of new asymmetric poly(phenylenevinylene) dendritic macromolecules using a stepwise convergent-growth approach is described. By an iterative methodology that made use of the Horner-Wadsworth-Emmons (HWE) reaction, dendrons and dendrimers up to the third generation, with eight different functional groups located at the periphery, were prepared in good yields. Both the number and placement of functionalities can be accurately controlled to afford a large variety of dendritic architectures.