The invention discloses five crystalline form substances of dihydromyricelin (of which the chemical name is 3,5,7,3',4',5'-hexahydroxy-2,3-dihydroflavonol and the English name is dihydromyricelin or ampelopsin). The spatial configuration of dihydromyricelin is characterized by virtue of colorimetry-polarimetry and high-performance liquid-phase chiral separation methods. By virtue of solid-state analytical technologies including a powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), a Karl Fischer titration and Fourier transform-attenuated total reflectance (FT-ATR) infrared spectroscopy, the crystalline forms of dihydromyricelin are characterized. The polymorph screening of dihydromyricelin is of important significance for the development of processes of active pharmaceutical ingredients, the development of dosage forms such as solid preparation, semi-solid preparation and suspension and quality control.