The first member, Y(OH)(BH)Cl·4.98HO, of a new family of boron-containing substances, closo-dodecaborate intercalated layered rare-earth hydroxides, was synthesized using a microwave-assisted hydrothermal method. The structure and composition of this compound were studied by X-ray diffraction, transmission and scanning electron microscopy, thermal analysis, inductively coupled plasma mass spectrometry, IR spectroscopy, and X-ray photoelectron spectroscopy. The title compound had the composition Y(OH)(BH)Cl·4.98HO and crystallized in a form of plate-like, aggregated particles less than 10 nm thick. The coordination of closo-dodecaborate anions with yttrium hydroxide host layers was demonstrated.