Layer-by-layer (LbL) assembly provides a facile approach in fabricating well-defined nanoarchitectures with electrical and electrochemical properties. Research on electrical and electrochemical performances of the LbL membranes from graphene oxide would be profound in modern photovoltaic nanodevices. We demonstrate here the LbL self-assembly of polyaniline-(grapheneoxide/polyaniline)(n) [PANi-(GO/PANi)(n)] (n represents the deposition cycle) multilayer films with good electrical and electrochemical behaviors and employment as counter electrodes (CEs) in dye-sensitized solar cells (DSSCs). The resulting multilayer films give a linear growth in bulk conductivity and increased electrocatalytic activity toward triiodides. Careful examination of data and characterizations indicates that the electrical and electrochemical properties are impressive to fulfill the task of PANi-(GO/PANi)(n) CEs. A promising power conversion efficiency of 7.41% (measured under standard AM1.5 test conditions) is obtained in PANi-(GO/PANi)(4) CE in comparison with 6.37% from PANi-(GO/PANi)(1) CE. This strategy provides new opportunity for the fabrication of efficient DSSCs, and the efficiency record is expected to be surpassed by scalable technique and components. (C) 2014 Elsevier Ltd. All rights reserved.