A novel sodium lead pentaborate, NaPbB5O9, has been successfully synthesized by standard solid-state reaction. The single-crystal X-ray structural analysis showed that NaPbB5O9 crystallizes in the monoclinic space group P21/c with a=6.5324(10) A˚, b=13.0234(2) A˚, c=8.5838(10) A˚, β=104.971(10)°, and Z=4. The crystal structure is composed of double ring [B5O 9]3- units, [PbO7] and [NaO7] polyhedra. [B5O9]3- groups connect with each other forming two-dimensional infinite ∞[B5O 9]3- layers, while [PbO7] and [NaO7] polyhedra are located between the layers. [PbO7] polyhedra linked together via corner-sharing O atom forming novel infinite ∞[PbO6] chains along the c axis. The thermal behavior, IR spectrum and the optical diffuse reflectance spectrum of NaPbB 5O9 were reported.