The flexible sponge/epoxy composite can wrap underwater artefacts in any shape and forms a protective shell after curing, thus effectively wrapping and reinforcing the artefacts. However, the hydroscopicity of the sponge itself limits the underwater application of the sponge/epoxy composite. In this study, a novel polyurethane sponge was prepared by modified with super‐hydrophobic multi‐wall carbon nanotubes (SH‐MWCNTs@PU sponge). Compared with the pristine PU sponge, the water‐contact angle on the surface of SH‐MWCNTs@PU sponges increased from 103.3 ± 1.82 to 152.6 ± 1.54o, and oily epoxy resin was able to cover the surface completely. The study shows that when SH‐MWCNTs@PU sponges/epoxy resin composite material is used underwater, it prevents both water from entering the sponge and also the inside epoxy resin from overflowing into the water. Moreover, the composite materials have excellent toughness after reinforcement under water (flexural strength = 3.56 MPa) and the soft sponges can be moulded to wrap any type of underwater artefacts. In the laboratory, when taking a broken, three‐dimensional blue‐and‐white porcelain pot as a research subject, the entire retrieval process—temporary stabilization, packaging, extraction and reinforcement material removal—was simulated to evaluate systematically all the technological aspects of safely excavating fragile underwater relics.