Porphyrins are very important chromophores as sensitizer in solar cell. Hole and electron transport layers are being used as an important layer to move the electrons and holes away from the sensitizer molecule to electrodes. In this work, a simple process has been developed for the synthesis of one layer combination of sensitizer and hole transport, that is, polyaniline-porphyrin (PANI-TPPS4) system as a bulk heterojunction. Macrospheres of fluorescent PANI-TPPS4 materials were synthesized by one-pot as well as two step processes directly from porphyrin for the first time. The advantage of this process is no need to isolate sulfonated porphyrin (TPPS4), which is a difficult process. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012