In this work, alkaline hydrogen evolution reaction (HER) processes of three typical nickel-based electrocatalysts [i.e., Ni, alpha-Ni(OH)(2), and beta-Ni(OH)(2)] were investigated to probe critical factors that determine the activity and durability. The HER activity trend was observed as Ni >>alpha-Ni(OH)(2) > beta-Ni(OH)(2), likely attributed to a synergy between metallic Ni and Ni(OH)(2) components on the Ni surface and fast water dissociation kinetics on the alpha-Ni(OH)(2) surface. With the HER proceeding, the metallic Ni surface, however, gradually became alpha-Ni(OH)(2), and alpha-Ni(OH)(2) surface ultimately transformed into beta-phase, leading to a dramatic activity decrease of Ni electrodes. Therefore, Ni electrodes were coated with alpha-Ni(OH)(2) nanosheets to slow down the nickel hydroxylation and optimize the surface ratio of Ni(OH)(2) to metallic Ni. This simple coating procedure enhanced both activity and durability of Ni electrocatalysts.