Mixtures of pentacene (PEN) and perfluoropentacene (PFP) were investigated via TEM. The diffraction pattern of the formed mixed phase is presented for the first time. The crystal structure of the mixed phase is similar to the one of PEN. Excess of PFP leads to long fibers on a background layer of the mixed phase. Excess of PEN results in PEN and mixed phase grains with sizes of (10–60) nm.