What is essential to solving energy scarcity problems is that develop the high activity, durable and non-noble metal-based dual-functional electrocatalysts for hydrogen evolution reactions (HER) and oxygen evolution reactions (OER). In this work, a series of core-shell structure M@Fe–Cu-GR nanocubes (NCs) are prepared. In the prepared process, the bimetallic FeCu prussian blue analogues (PBA) is used as precursor, transition metals ions Co2+ and Ni2+ are introduced into the FeCu-PBA using the exchange of potassium ions with other metal ions, and then the FeCu-PBA are successfully loaded on the graphene oxide (GO) employed the attraction of opposite charges between polydiallyldimethylammonium chloride (PDDA) and GO. Electrochemical tests show that the Tafel slope of Co–Ni@Fe–Cu–GR NCs for HER and OER are 60 and 82 mV dec−1, respectively, and Co–Ni@Fe–Cu–GR NCs shows excellent performance in long-term stability test.