Abstract <p>An approach to growing Li₄Mo₅O₁₇ crystals by the low-thermal-gradient Czochralski technique (LTG CZ) was optimized to obtain bulk single crystals with dimensions 70×35×35&#xa0;mm. An alteration of temperature parameters during the crystal growth process was proposed. Faceting was studied on a number of Li₄Mo₅O₁₇ crystals grown under varying conditions, Miller indexes of the developed facet families were determined, and based on the obtained data, a reference model of Li₄Mo₅O₁₇ crystal was visualized. Molybdenum coordination in Li₄Mo₅O₁₇ crystal was studied by X-ray photoelectron spectroscopy. X-ray diffraction patterns of Li₄Mo₅O₁₇ were recorded in the temperature range of 323-743&#xa0;K. Based on obtaining data, thermal expansion vectors were calculated and an expansion ellipsoid was visualized.</p>