In the su(2|2) spin chain motivated by the AdS/CFT correspondence, a novel symmetry extending the superalgebra su(2|2) into u(2|2) was found. We pursue the origin of this symmetry in the exceptional superalgebra d(2, 1; ε), which recovers su(2|2) when the parameter ε is taken to zero. Especially, we rederive the Yangian symmetries of the AdS/CFT spin chain using the exceptional superalgebra and find that the ε-correction corresponds to the novel symmetry. Also, we reproduce the non-canonical classical r-matrix of the AdS/CFT spin chain expressed with this symmetry from the canonical one of the exceptional algebra.