The octanuclear complex [Eu8L4(1,4-BDC)(2)Cl-8(MeOH)(12)]center dot 4Cl center dot 2MeOH-18H(2)O (2) was obtained from the reaction of the tetranuclear Eu(III) species [Eu4L2Cl2(OH)(4)(H2O)(4)(MeOH)(2)]center dot 2Cl center dot 7MeOH center dot 2H(2)O (1) and 1,4-H2BDC (H2L = bis(5-bromo-3-methoxysalicylidene)ethylene-1,2-phenylenediamine, 1,4-H2BDC = 1,4-benzenedicarboxylic acid). Both 1 and 2 were structurally characterized by X-ray crystallography, and their luminescence properties were determined. The cagelike structure of 2 encapsulates two chloride anions via MeOH center dot center dot center dot Cl hydrogen bonding. In the solid state, 2 has an open three-dimensional network with extended channels and is capable of reversible MeOH adsorption.