Multi-walled carbon nanotubes (MWCNTs) were purified by concentrated nitric acid and sulfuric acid. MWCNTs/Zn0.96Co0.04O composite nanofibers were prepared through electrospinning and calcination technique. The crystalline phase and micromorphology of the samples were examined by TGA, XRD, FT-IR, SEM and TEM. Microwave absorption properties and infrared emissivity of MWCNTs/Zn0.96Co0.04O composite nanofibers were determined with a vector network analyzer and a IR-2 infrared emissivity analyzer respectively. The results showed that the average diameter of MWCNTs/Zn0.96Co0.04O composite nanofibers were about 160nm. The lowest infrared emissivity of MWCNTs/Zn0.96Co0.04O composite nanofibers was 0.61, at which the mass fraction of MWCNTs was 6%. The matching thickness of MWCNTs/Zn0.96Co0.04O composite nanofibers was 1.5mm, at which the microwave absorption properties were fine: The minimum reflection could reach -26.4 dB at 13.8 GHz, and the frequency band with reflectivity less than -10 dB was 11.8～15.8 GHz. It is possible that MWCNTs/Zn0.96Co0.04O composite nanofibers were used as a novel and promising infrared/radar compatible stealth material.