Hybrid conjugated systems consisting of a triphenylamine core substituted by three dithiafulvenyl moieties have been synthesized and tested as active materials in organic field-effect transistors and photovoltaic devices. UV–vis. spectroscopy studies demonstrate that, despite their amorphous character shown by X-ray diffraction and differential scanning calorimetry, strong interactions exist in these materials as an aggregative band is observed at low energies. A first evaluation of their potentialities as p semiconductor in organic field-effect transistors shows significant hole mobilities. For bilayer photovoltaic devices, a power conversion efficiency of 0.11% is observed and the external quantum efficiency of the cell under monochromatic irradiation shows a non-negligible contribution of the aggregative band.