A novel polymer electrode is prepared by incorporating polyimide (PI) with chemical reduced graphene oxide (rGO). Then modified this PI/RGO electrode with a layer of electrochemical-reduced graphene oxide (EGO), and by this way the expected EGO/PI/RGO electrode is obtained. Compared with bare PI/RGO film, the hybrid EGO/PI/RGO electrode own large active area and excellent conductivity, which offers more extensive field to prepare compound and more sensitive surface to detect electrochemical signal. SnSe is prepared on this modified substrate by electrochemical atomic layer deposition (EC-ALD) technology. Moreover, SnSe deposit on bare PI/RGO electrode by EC-ALD method is also done for comparison. Open-circuit potential (OCP) and Mott-Schottky measurement indicated the obtained SnSe is a p-type semiconductor. Moreover, the semiconductor appears more excellent photoelectric property on modified electrode. (C) 2013 Elsevier Ltd. All rights reserved.