Novel nickel hierarchical structures were prepared through a facile one-pot solvothermal approach in the presence of surfactant and mineralizer. The influence of dynamics factors such as polyvinylpyrrolidone (PVP) content, ratio (R) between NaF and NH₃·H₂O on the morphologies of the as-synthesized products were investigated in detail. By regulating the dynamics factors, nickel crystals with three different structures (hcp and fcc mixture structure, fcc structure and a mostly hcp structure) were synthesized. Meanwhile, the corresponding morphologies are changed from hierarchical structures composed of nanoparticles to hierarchical structures consisted of nanoflakes, and to polyhedra. The values of saturation magnetizations of nickel crystals also range from 41.6 to 8 emu g⁻¹ because of the change of crystal structure from fcc to mostly hcp. One thing to be mentioned is that the mostly hcp phase can be completely converted into fcc phase if the solvothermal treatment temperature is further enhanced to 220 °C. Further, the Congo red (CR) removal ability by the as-obtained nickel particles was evaluated. By the investigation of adsorption and desorption experiments on nickel powders, we can ascertain that chemical reduction and physical adsorption happen at the same time during the treatment process of CR solution.