A number of Eu-doped layered yttrium hydroxides intercalated with various benzenedicarboxylate (phthalate, isophthalate and terephthalate) and sulphobenzoate (2-, 3- and 4-sulphobenzoate) anions were obtained using hydrothermal microwave (HTMW) treatment. For the first time, phthalate, isophthalate and sulphobenzoate anions were intercalated into layered rare-earth hydroxides (LRHs). Two approaches for the synthesis of intercalated layered yttrium hydroxides were used: ion exchange reactions and homogeneous hydrolysis of rare-earth cations in the presence of intercalated anions. Ion-exchange reactions between layered rare-earth hydroxides and a series of benzenedicarboxylic and sulphobenzoic acid salts were performed under the conditions of HTMW treatment, which significantly increased the rate of intercalation. The structure of the first representative of layered rare-earth hydroxides intercalated with sulphobenzoate-type anions, namely layered yttrium hydroxide intercalated with 4-sulphobenzoate of the composition Y3(OH)7(C7H4O5S)·H2O, was solved. Intercalation of benzenedicarboxylate and sulphobenzoate anions into Eu-doped layered yttrium hydroxides led to a substantial sensitization of Eu3+ luminescence. The local symmetry of Eu3+ was greatly decreased by intercalation of benzenedicarboxylate and sulphobenzoate anions.