Since the first report of high energy conversion efficiencies for dye sensitized TiO2 solar cell, a great deal of work was devoted to understand the interfacial electron transfer phenomena and to increase the cell performance. In order to increase the cell efficiency, systematic piling-up of photon harvesting dye molecules on the surface of semiconductor, such as multilayer sensitization, was proposed. The multilayer structure of certain molecule forms a hole or column that can be occupied by an electro active guest molecule and the resulting composite might facilitate electron transfer. Polyaniline is a conducting polymer that has been widely studied for the electronic and optical application. Polyaniline has five basic structures (leucoemeraldine, protoemeraldine, emeraldine, nigrraniline, pernigraniline) with different oxidation states, which are chemically and electrochemically switchable. This unique property of polyaniline can be utilized in electron transfer process, serving as either electron acceptor (hole acceptance), or electron donor (hole injection) depending on the relative positions of redox potential of exited dye molecule and polyaniline. In this work, we report the procedure for assemblies of porphyrin multilayer as dyes on ITO (indium-thin oxide) and electropolymerization of aniline as conductive material inside porphyrin building blocks. Porphyrin units are assembled layer-by-layer by zirconium phosphonate (ZrP) linkage and polyaniline is electrochemically packed inside the porous films.