The anatase TiO(2) pillar (PL)-TiO(2) nanoparticle (NP) composite is fabricated via layer-by-layer assembly. The composition of the nanostructures (i.e. the pillar-to-nanoparticle ratio) can be conveniently tuned by controlling the experimental conditions of the layer-by-layer assembly. It has been used to fabricate photoelectrodes for high-efficiency dye-sensitized solar cells (DSSCs), which combine the advantages of the rapid electron transport in PLs with the high surface area of NPs. It was found that, with optimum preparation conditions, DSSCs with the composite photoelectrode show a better photoelectrical conversion efficiency (8.06%) than those with either the naked PL photoelectrode or the mechanically mixed PL-NP photoelectrode. This is explained by the photoelectron injection drive force and the interfacial electron transport of the DSSCs, which are quantitatively characterized using the surface photovoltage spectra and electrochemical impedance spectroscopy measurements. It is evident that the DSSC with the optimal PL/NP ratio displays the largest photoelectron injection drive force and the fastest interfacial electron transfer.