In this work, Eu-containing poly (vinyl acetate) and poly (vinyl alcohol) are made into triple physical cross-linked hydrogels. The hydrogels exhibit good tensile strength, ultrahigh toughness, excellent compressive recovery and identifiability. The superior mechanical properties of the hydrogels originate from the synergetic interactions of hydrogen bonding, molecular crystals, and hydrophobic interactions. The hydrogels are identifiable due to the introduction of the Eu(iii) organic complex [Eu(DBM)2(Phen)MA] into vinyl acetate and the identifiability of the hydrogel proves the uniformity of two types of polymers (Eu-PVAc and PVA) in the hydrogels. This strategy not only provides a new idea for the synthesis of the hydrogel containing hydrophilic and hydrophobic materials but also opens an avenue to fabricate multifunctional hydrogels applied in the field of bio-sensors, biological imaging, drug delivery and tissue engineering.