A confined Ni(0) nanocatalyst derived from NiAl-layered double hydroxide (NiAl-LDH), with ultrafine Ni nanoparticles implanted in the NixAlyO support, was first fabricated by the urea coprecipitation method using pine pollen as a biotemplate, together with subsequent calcination/reduction process. This hollow biotemplate-assisted catalyst displayed high phenol-hydrogenation activity and stability, which can be ascribed to its higher surface area, better dispersibility, and ultrafine Ni particle size. The hollow morphology and confinement effect of lamellar NiAl-LDH can not only lead to better dispersion of the active Ni(0) species, but also strengthen the interaction between Ni(0) species and NixAlyO support. This protocol can overcome the shortcomings of conventional LDH-derived catalysts that lack specifically shaped morphology and hierarchical structure, inhibiting the aggregation of the Ni nanoparticles, hence resulting in its good activity and stability.