Pb2[B5O9]Br borate powder was synthesized by the high-temperature solid-state method. The transparent single crystal of Pb2[B5O9]Br was grown by top-seeded solution growth method using the powder as raw material. The typical crystal size was about 3 mm×3 mm×1.5 mm. X-ray diffraction analysis show that it is same as the one reported in the literature. It belongs to the orthorhombic system, space group Pnn2, and lattice parameters a=1.1524(1) nm, b=1.1431(1) nm, c=0.65399(3) nm. The measurement of the infrared spectrum indicate that the basic anionic group is the BO33- and BO45-. The reflection spectrum show that the cut-off wavelength of Pb2[B5O9]Br is about 250 nm. Pb2[B5O9]Br exhibits a powder second harmonic generation (SHG) effect similar to that of β-BaB2O4.