A new photoluminescent bimetallic-3-hydroxypicolinate/graphene oxide composite was prepared by incorporation of the complex Na₅[EuW₂O₆(picOH)₈] (1; HpicOH being 3-hydroxypicolinic acid) on graphene oxide (GO). Photoluminescence studies (emission and excitation spectra and ⁵D₀ emission decay curves) were performed on 1 and the composite 1/GO suggesting an effective interaction between the picOH⁻ ligands and the graphene oxide.