Three novel alkaline earth metal benzene-1,4-dioxylacetates M(L)H 2 O (M=Ca, Sr or Ba, L=benzene-1,4-dioxylacetate) with three-dimensional (3D) hybrid frameworks were reported. Both Ca(L)H 2 O (1) and Sr(L)H 2 O (2) crystallize in the monoclinic space group P2 1 /c while Ba(L)H 2 O (3) in the monoclinic space group P2 1 . As determined by X-ray single-crystal analysis, in these compounds each metal ion is coordinated by eight O atoms: four from different carboxylate groups, two from one carboxylate group, one from the ether oxygen and one from one water molecule. Each L 2− ligand coordinates to five alkaline earth metal centers through one of its ether oxygen atoms and two carboxylate groups adopting novel μ 3 -η 2 :η 2 -bridging and μ 2 -η 1 :η 1 -bridging coordination modes to give rise to a 3D network. The luminescence analysis shows that complexes 1 and 2 exhibit fluorescence in the solid state at room temperature.