The first synthesis of a semiconductor hybrid diblock copolymer comprised of p-type dendritic and n-type linear blocks by nitroxide mediated radical polymerization (NMRP) is reported. A triphenylamine (TPA) bearing second generation polyether dendron [G2]-OH has been functionalized with an alkoxyamine and, subsequently, perylene bisimide acrylate (PerAcr) was polymerized to obtain a hybrid block copolymer, [G2]-b-PPerAcr. The hybrid block copolymer structure is supported by (1) H NMR and size exclusion chromatography. Furthermore, the novel materials were studied by UV-vis absorption spectrometry, photoluminescence, cyclic voltammetry, differential scanning calorimetry and thermogravimetry analysis.