In this work we report on functional multilayer films containing electrochemically reduced graphene oxide (ERGO) by the alternating layer-by-layer (LBL) assembly of negatively charged graphene oxide (GO) and positively charged poly (diallyldimethylammonium chloride) (PDDA) in combination with an electrochemical reduction procedure. As a metal-free catalyst, the resulting [PDDA@ERGO] multilayer film possesses a remarkable electro-catalytic activity toward the oxygen reduction reaction (ORR) with superior methanol tolerance in alkaline media. Further research indicates that the unusual catalytic activity of the prepared hybrid films arises from synergetic chemical coupling effects between PDDA and ERGO. Importantly, the [PDDA@ERGO] multilayer film as a metal free oxygen reduction catalyst reported here is easy to build up with the advantages of fine control of the film thickness, being energy effective, fast and green without using dangerous and corrosive substances.