An NiAl-layered double-hydroxide (NiAl-LDH) nanosheet array is grown on a graphene oxide (GO) substrate (NiAl-LDH@GO) by the hydrothermal method. The NiAl-LDH@GO is used as the precursor to synthetize an N-doped carbon@Ni–Al2O3 nanosheet array@GO composite (N–C@Ni–Al2O3@GO) by coating with dopamine followed by calcination. The N–C@Ni–Al2O3@GO is used as a non-noble metal electrocatalyst for hydrogen evolution reaction in alkaline medium, and exhibits high electrocatalytic activity with low onset overpotential (−75 mV). The improved electrocatalytic performance of N–C@Ni–Al2O3@GO arises from its intrinsic features. First, it has a high specific surface area with the Ni nanoparticles in the composite dispersed well and the sizes of Ni nanoparticles are small, which lead to the exposure of more active sites for electrocatalysis. Second, there is a synergistic effect between the Ni nanoparticles and the N–C coating layer, which is beneficial to reduce the activation energy of the Volmer step and improve the electrocatalytic activity. Third, the N–C coating layer and the XC-72 additive can form an electrically conductive network, which serves as a bridge for the transfer of electrons from the electrode to the Ni nanoparticles.