A new kind of Ni-Cu-coated calcium-magnesium silicate whiskers was prepared by electroless plating and characterized by EDS, SEM and XRD. And the preparation and shielding performance of a new kind of Ni-Cu-coated calcium-magnesium silicate whisker/nickel powder/epoxy resin electromagnetic shielding coatings were explained. The study results show the Ni-Cu-coated whisker with micro-sized spinal structure contains 12.4 wt% Ni and 1.35 wt% Cu. When the coating layer thickness is 300 μm, the shielding effectiveness of the coatings containing 4 wt% Ni-Cu-coated calcium-magnesium silicate whisker is up to 39.24-48.52 dB and increased an average of 10.38 dB compared with the nickel powder/epoxy resin electromagnetic shielding coatings in the frequency range of 0.3-1000 MHz. This offers a new idea to raise the levels of the comprehensive utilization of mineral resources and the prevention of electromagnetic environmental pollution.