Porous sea urchin-like nickel-doped ZnO with various nickel contents and high specific surface area were synthesized using a solution method followed by calcination. The nickel-doped ZnO products consisted of numerous porous nanoleaves. The Ni content in these products ranged from 5% to 20%. The Ni dopants in the ZnO lattice were verified by X-ray diffraction and X-ray photoelectron spectroscopy. The sensors based on nickel-doped ZnO sea urchins showed superior sensing performance for some volatile organic compounds (VOCs). ZnO sea urchins with 10% nickel doping exhibited the best gas-sensing performance, including a low working temperature, short response/recovery time, and high sensor response. In particular, the 10% Ni-doped ZnO sea urchin sensor exhibited a response of 84.4 with response/recovery times of 17/20 s towards 100 ppm formaldehyde vapor. These superior sensing behaviors were attributed mainly to a suitable Ni content with high content of oxygen defects, small nanocrystals, and a porous hierarchical structure with a high specific surface area.