Despite flexible and wearable electromagnetic interference (EMI) shielding fabrics have aroused accelerated attention in recent years, problem such as detachment caused by traditional physical bonding methods still remains a huge challenge. Click chemistry, as a type of chemical reaction that generate substances by joining small units together with heteroatom links, is an emerging surface modification technology. Herein, thiol-epoxy click chemistry is utilized to connect thiol-modified carbon nanotubes (CNTs) and cotton/spandex blended fabric (CSF). The resultant fabric exhibits good hydrophobicity with water contact angle of 121.4° in conjunction with a high X-band shielding effectiveness (SE) of 27.30 dB with coating thickness of only ~140 μm. More importantly, benefiting from the constructed strong chemical bond with CNTs coating and fiber, the obtained fabric shows high resistance to bending test, strong acid/alkali solutions (pH = 2.0/12.0), liquid nitrogen and so on. Our work demonstrates that the EMI shielding fabrics with excellent corrosion resistance and stability prepared by thiol-epoxy click chemistry potentially suitable for long-term EMI shielding applications even in extreme environments.