In this study, novel porous hollow Ni/SnO2 hybrids were prepared by a facile and flexible two-step approach composed of solution reduction and subsequent reaction-induced acid corrosion. In our protocol, it can be found that the hydrothermal temperature exerts a vital influence on the phase crystal and morphology of Ni/SnO2 hybrids. Notably, the Ni microspheres might be completely corroded in the hydrothermal process at 220 °C. The complex permittivity and permeability of Ni/SnO2 hybrids-paraffin wax composite were measured based on a vector network analyzer in the frequency range of 1-18 GHz. Electromagnetic absorption properties of samples were evaluated by transmission line theory. Ni/SnO2 hybrid composites exhibit superior electromagnetic absorption properties in comparison with pristine Ni microspheres. The outstanding electromagnetic absorption performances can be observed for the hollow porous Ni/SnO2 hybrid prepared at 200 °C. The minimum reflection loss is -36.7 dB at 12.3 GHz, and the effective electromagnetic wave absorption band (RL < -10 dB, 90% microwave attenuation) was in the frequency range of 10.6-14.0 GHz with a thin thickness of 1.7 mm. Excellent electromagnetic absorption properties were assigned to the improved impedance match, more interfacial polarization and unique hollow porous structures, which can result in microwave multi-reflection and scattering. This novel hollow porous hybrid is an attractive candidate for new types of high performance electromagnetic wave-absorbing materials, which satisfies the current requirements of electromagnetic absorbing materials, which include wide-band absorption, high-efficiency absorption capability, thin thickness and light weight.