Carbon nanotubes (CNTs) are widely utilized as conductive fillers due to their high conductivity, lightweight, and ease of modification. However, their poor dispersion limits their otherwise excellent performance. In this study, we successfully prepared a high toughness, strong electromagnetic interference (EMI) shielding hydrogel by blending polyvinyl alcohol (PVA) hydrogel with multi‐walled carbon nanotubes (MWCNTs) modified by anionic surfactant sodium dodecylbenzene sulfonate (SDBS) and (3‐aminopropyl) triethoxysilane (KH550). We found that the modifiers can not only promote the uniform dispersion of MWCNTs but also improve the mechanical properties of the hydrogel. The results demonstrate that the stress (≈14.86 MPA), elongation at break (233.9%), and compressive strength (≈2.89 MPA) of PVA/MWCNTs composite hydrogel with 1 wt% MWCNTs and 5 wt% PVA were increased by 533.6%, 241.4%, and 206.5%, respectively. Encouragingly, the total electromagnetic shielding effectiveness (SET) is 123.6 dB at a thickness of 5 mm. In summary, this work provides a general approach to functionalizing MWCNTs, which has great potential for developing EMI shielding materials with high toughness.