Hexagonal yttrium hydroxide fluoride microcrystals were prepared by a two-step hydrothermal route using yttrium nitrate, sodium hydroxide and sodium fluoride as raw materials to react in propanetriol solvent. The samples were characterized by powder X-ray diffraction (XRD), energy dispersive spectrum (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier trans-form infrared spectroscopy (FT-IR), thermogravimetre and differential-thermogravimetric analysis (TG-DTA), which revealed that Y(OH)2.14F0.86 microcrystals were multi-branched and that the branches of Y(OH)2.14F0.86 microcrystals were composed of hierarchical tubes. This novel multi-branched and intriguing hierarchical tubular structure of yttrium hydroxide fluoride maybe has a potential application in photoelectric crystals. The formation of branched Y(OH)2.14F0.86 microcrystals with hierarchical tubular structure were due to the substitution reaction and Oswald ripening. Hexagonal yttrium hydroxide fluoride microcrystals were prepared by a two-step hydrothermal route using yttrium nitrate, sodium hydroxide and sodium fluoride as raw materials to react in propanetriol solvent. The samples were characterized by powder X-ray diffraction (XRD), energy dispersive spectrum EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier trans-form infrared spectroscopy (FT-IR), thermogravimetre and differential- thermogravimetric analysis (TG- DTA), which revealed that Y This novel multi-branched and intriguing hierarchical tubular structure of yttrium hydroxide fluoride maybe has a potential application in photoelectric crystals. The formation of branched Y (OH) 2.14F0.86 microcrystals with hierarchical tubular structure were due to the substitution reaction and Oswald ripening.