Large crystals of Na-5[B2P3O13] with dimensions of 22 x 24 x 17 mm(3) and 35x 15x5mm(3) have been grown by the Kyropouls and Czochralski methods respectively for the first time. Parameters of crystal growth including the seed direction, cooling rate and rotation rate were investigated. The measured transmittance spectrum from 180 nm to 2800 nm indicates that the absorption edge lies at 186 nm. Furthermore, Na-5[B2P3O13] crystal exhibits an optical second harmonic generation effect about the same as that of KDP(KH2PO4).