A templated borate [Hdmpip][B 5 O 6 (OH) 4 ] (dmpip = 1,4-dimethylpiperazine) has been synthesized and characterized by single crystal X-ray analysis, element analysis, IR spectroscopy, PXRD, TG-DSC, EPR, luminescence spectroscopy, and quantum chemistry analysis. The title compound contains the [B 5 O 6 (OH) 4 ] -anions that are connected together by O-HÁÁÁH H-bonds to form a 3-D network with 1-D tunnels, in which [Hdmpip] ? cations were located in. The luminescence spectra of [C 9 H 14 N]Á[B 5 O 6 (OH) 4 ] showed tunable luminescence emission by means of annealing treatment from 150 to 360°C.