Recent progress in Cs2HfCl6 (CHC) crystal production achieved within the last five years is presented. Various aspects have been analyzed, including the chemical purity of raw materials, purification methods, optimization of the growth and thermal conditions, crystal characterization, defect structure, and internal radioactive background. Large volume, crack-free, and high quality CHC crystals with an ultimate scintillating performance were produced as a result of such extensive research and development (R & D) program. For example, the CHC crystal sample with dimensions ∅23 × 30 mm3 demonstrates energy resolution of 3.2% FWHM at 662 keV, the relative light output at the level of 30,000 ph/MeV and excellent linearity down to 20 keV. Additionally, this material exhibits excellent pulse shape discrimination ability and low internal background of less than 1 Bq/kg. Furthermore, attempts to produce a high quality CHC crystal resulted in research on this material optimization by constitution of either alkali ions (Cs to Tl), or main element (Hf to Zr), or halogen ions (Cl to Br, I, or their mixture in different ratio), as well as doping with various active ions (Te4+, Ce3+, Eu3+, etc.). This leads to a range of new established scintillating materials, such as Tl2HfCl6, Tl2ZrCl6, Cs2HfCl4Br2, Cs2HfCl3Br3, Cs2ZrCl6, and Cs2HfI6. To exploit the whole potential of these compounds, detailed studies of the material’s fundamental properties, and understanding of the variety of the luminescence mechanisms are required. This will help to understand the origin of the high light yield and possible paths to further extend it. Perspectives of CHC crystals and related materials as detectors for rare nuclear processes are also discussed.