The main processes for preparing bulk single crystals and films of photorefractive and piezoelectric Bi 12 M x O 20 ± δ (M = Group II-VIII elements) sillenite compounds are considered. Experimental data are summarized on the crystal growth of Bi 12 M x O 20 ± δ from the melt and under hydrothermal conditions, and the key morphological features of sillenites are analyzed. Various types of macroscopic growth defects in sillenite-type crystals are described, and their origin is discussed. The compositions of second-phase inclusions in undoped and doped (Group I-VIII elements) Bi 12 SiO 20 , Bi 12 GeO 20 , and Bi 12 TiO 20 single crystals are presented, and the main physicochemical properties of various Bi 12 M x O 20 ± δ crystals are summarized.