In the present work, polymerization of monomer diaminonaphthalene (DAN) was carried out inside the poly (vinyl alcohol) (PVA) film that resulted in the formation of multi inter-phases of the two polymers. The presence of functional groups of the PVA and PDAN in the blend film was confirmed by the FTIR spectra. The formation of multi-interphases was further confirmed by the ToF-SIMS technique. The positive ion beam spectra of the prepared polymer matrix provided insights about the morphology of the top most layer and the interphases layers developed within the polymer blend film. The formation of multi inter-phases offered potential in designing bulk hetero-junction semiconductor structures. (C) 2017 Elsevier Ltd. All rights reserved.