Owing to the widespread use of electronic devices, energy harvesting technologies have attracted enormous attention to fulfill the soaring energy demands. Considering this, a generator based on the magnetoelectric (ME) effect is proposed as a promising energy harvesting device. As one class of ME materials, polymer-based ME laminates consisting of piezoelectric (PE) and magnetostrictive (MS) phases convert magnetic fields to electric voltage by strain transfer between the PE and MS phases. Herein, P(VDF-TrFE)/nano-porous Ni (P/np-Ni) binderless laminates were designed to investigate the ME voltage in polymer-based ME laminates by regulating the surface morphology of MS substrate. To implement a binderless state, nano-porous Ni (np-Ni) substrates were prepared via an electrochemical treatment. The morphology of np-Ni substrates was electrochemically adjusted with different treatment conditions. As a result, from P/np-Ni binderless laminates, an optimal ME coefficient of 8.41 (±1.00) mV/cm•Oe was achieved by a stable physical adhesion between the PE polymer and MS nano-porous structures. Moreover, the different ME voltage tendency according to interfacial morphology in the binderless laminates demonstrates the suitable interface configuration for polymer-based ME laminates as energy harvesting devices.