The single crystal structure of hexabenzylhexaazaisowurtzitane (HBIW) was determined by X-ray single crystal diffractomater, the characteristics of NMR spectra of HBIW were studied in CDCl₃, acetone-d₆ and DMSO-d₆, respectively, and the molecular structure of HBIW was identified by a combination of 1D (¹H NMR, ¹³C NMR and ¹⁵N NMR) and 2D (gHSQC and gHMBC) NMR techniques. Results show that the crystal belongs to orthorhombic system with space group Pca2(1) and the unit cell parameters a=0.10724(2) nm, b=0.37001(7) nm, c=0.20476(4) nm, α=β=γ=90°, V=8.125(3)×10³ nm³, Z=4, D_c=1.159 g·cm^-3, F(000)＝3024. The chemical shifts of H atoms from high field to low field are assigned to CH on the bridge head, CH₂ bonded to six-membered ring, CH₂ bonded to five-membered ring, CH in six-membered ring and CH in benzene, respectively, while the chemical shifts of C atoms from high field to low field are assigned to CH₂ bonded to five-membered ring, CH₂ bonded to six-membered ring, CH in six-membered ring, CH on the bridge head, and C in benzene. The chemical shifts of N atoms in five-membered ring and six-membered ring ware found at δ =-317.0 and δ =-297.1, respectively.