We report the synthesis of needle-shaped nanocrystals of Ni(5)TiO(7) utilizing a solid-phase reaction of NiO with a porous and rough TiO(2) surface produced by plasma electrolytic oxidation. The single crystalline orthorhombic nanocrystals are grown along the [010] axis, featuring a length of ∼10 μm and diameters varying from several tens of nanometers up to 200 nm. The resulted novel Ni(5)TiO(7)/TiO(2)/Ti nanoarchitectured compound composite has been proven outstandingly active as a catalyst and appears most suitable for high-temperature operation in biomass gasification. The findings may pave the way to an improved and environmentally friendly technology of energy generation.