Electromagnetic shielding fabric (ESF) is a novel electromagnetic shielding product with portability, flexibility, and good mechanical properties. However, the existing ESFs suffer from poor washing fastness of coating and poor comfort performance in terms of hand-feel characteristic. In this study, a core layer-coated yarn (CLCY) was successfully spun using a carboxylic acid-functionalized multi-walled carbon nanotube/polypyrrole/Fe3O4 composite suspension with polyvinyl butyral as an adhesive agent. To better explore the properties, the original fabric and treated fabrics, viz., core layer-coated fabric (CLCF) and surface layer-coated fabric (SLCF), were characterized by several methods. Scanning electron microscopic observations revealed that the coating was on the core layer in CLCF. In addition, the Fourier-transform infrared spectroscopy and X-ray diffraction spectroscopy results revealed that the composition of the coating corresponds with that in the multi-composite suspension. Moreover, the coating of CLCY formed a conductive path with good conductivity in the core layer, but the conductivity of the coating on the surface layer of SLCF deteriorated sharply after washing. Further, compared with the original fabric and SLCF, CLCF has highest breaking strength (after 10 washes), and keeps a relatively good hand-feel characteristic. Finally, the evaluated electromagnetic interference shielding characteristics reveal that the fastness of coating affects the electromagnetic shielding effectiveness, suggesting that the wrapped protection of outside staple fibers in CLCF reduce the loss of coating in the core layer during washing. However, the coating on the surface layer in SLCF could be washed away easily.