As the most commonly used primary explosives， lead azide and lead styphnate are widely used in military and civilian applications. However， they are harmful to the environment and human body. Therefore， the research of new green primary explosives is an important trend. This paper reviews the synthesis and performances of six new types of initiating agents， including tetrazole， furazan， fused-ring， coordination compound， copper azide， and nano-thermite. Among of these initiating agents： （1） tetrazoles have excellent detonation performance but low safety performance； （2） furazans have higher density and good oxygen balance； （3） fused ring compounds have high thermal stability， low sensitivity and good safety； （4） the sensitivity and energy can be tailored by changing the metal ions， ligands and anions； （5） copper azide has strong detonation ability while its electrostatic sensitivity is extremely high； （6） nano-thermite has the merits of high energy density， ease of synthesis， and environment friendly， but it is difficult to achieve rapid combustion to detonation. Except for copper azide and nano-thermite， the other four types of primary explosives have complex synthesis processes and low yields. Therefore， the decreasing of sensitivity and process feasibility should be emphasized with the consideration of detonation ability for the further research of primary explosives.