Here we introduce a new strategy for synthesis of layered double hydroxide CoAl-LDH nanosheets and N-doped graphene composite via Successive Ionic Layer Deposition (SILD) method as well as the study of their efficiency as electrocatalytic materials for hydrogen evolution reaction in alkaline media. The synthesis nanosheets were characterized by SEM, EDX, XRD, Raman, XPS and FTIR methods. Electrocatalytic characteristics of electrodes based on nickel foil and nanosheets synthesized via SILD method (50 cycles) have been studied in 1 M KOH solution by using techniques of polarization curves, cyclic voltammetry and chronoamperometry. The values of excess voltage at the current density of 10 mА/cm ² for CoAl-LDH and N-doped graphene nanocomposite were −415 and −365 mV, and Tafel slope was 53 mV/dec and 48 mV/dec, respectively. We report that CoAl-LDH composite containing N-doped graphene shows better electrocatalytic characteristics than CoAl-LDH without graphene and has high cyclic stability.