Self-assembled submicron nickel particles were successfully synthesized via the one-step surfactant-assisted solvothermal method. The impact of surfactant and reducing agent stoichiometry is investigated in this manuscript. Different morphologies and structures of Ni particles, including flower-like nanoflakes, hydrangea-like structures, chain structures, sphere-like structures, and hollow structures were prepared through different processing conditions with two parameters such as temperature and time. Based on scanning electron microscopy (SEM), X-ray diffraction (XRD), thermal gravimetric analysis (TGA) and vibrating sample magnetometry (VSM), the submicron nickel particles show good saturation magnetization and excellent thermal stabilities with a possible growth mechanism for the variety of the structure-tuned formation. Importantly, the microwave absorption properties of the submicron nickel particles were studied. The lowest reflection loss of Ni-P₉/T₂₀₀/H₁₅ with a thin layer thickness of 1.7 mm can reach −42.6 dB at 17.3 GHz.