The templated borate, [C9H14N]·[B5O6(OH)4], was synthesized under hydrothermal conditions. Single crystal X-ray diffraction techonology reveals that it crystallizes in the triclinic system, space group P (No. 2). The material was also characterized by element analysis, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), thermogravimetric and differential thermal analysis (TG-DTA), and luminescence spectroscopy. The compound consisted of isolated pentaborate [B5O6(OH)4]– and N-butylpyridinium cations [C9H14N]+. The [B5O6(OH)4]– anions are connected together by hydrogen bonds to form a three-dimensional framework, in which [C9H14N]+ cations are located in. [C9H14N]·[B5O6(OH)4] exhibits tunable luminescence emission at 415–458 nm by means of heating treatment from 100 to 300 °C.