Novel Ca B O ·H O:Eu nanotubes, constructed with nanobelts, were prepared using a hydrothermal method. The Ca (BO ) :Eu nanobelts with a thickness of about 100 nm were made for the first time using a two-step hydrothermal process with Ca B O ·H O:Eu as the precursor. The samples were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetry differential thermal analysis and scanning electron microscopy. The relationship between Ca (BO ) :Eu and Ca B O ·H O:Eu was also studied. Possible reaction and growth mechanisms for Ca B O ·H O:Eu and Ca (BO ) :Eu were proposed. Ca (BO ) :Eu preserved the basic microstructure unit of Ca B O ·H O:Eu . Both Ca B O ·H O:Eu and Ca (BO ) :Eu exhibited red emissions centred at 614 nm, but the maximum excitation peaks for Ca B O ·H O:Eu and Ca (BO ) :Eu differed. Ca (BO ) :Eu exhibited higher photoluminescence intensity but a lower R/O value than Ca B O ·H O:Eu .