Chalcogenides have been widely used in the military and civilian infrared (IR) fields owing to their high nonlinear optical(NLO) coefficient and wide IR transparent ranges. Among them, diamond-like semiconductors(DLSs) exhibit the inherent noncentrosymmetrical(NCS) structure that can satisfy the prerequisite condition as one NLO material and I2-II-IV-VI4formula type (I=Li, Ag, Cu; II=Zn, Cd, Hg, Mg, Co, Fe; IV=Si, Ge, Sn;VI=S, Se) has become one of the important research systems. So far, 78 I2-II-IV-VI4 DL chalcogenides with NCS structures have been found in the above system, they crystallize in seven different space groups including Pmn21, Pna21, Pn, I4-, I4-2m, Cmc21, F222.This review systematically summarizes the structural characteristics and NLO properties of DLSs in different space groups and the result provides the theoretical guidance for the future exploration of IR NLO crystals with excellent performances.