The requirements for high energy and green primary explosives are more and more stringent because of the rising demand in the application of micro initiation explosive devices. Four new energetic compounds with powerful initiation ability are reported and their performances are experimentally proven as designed, including non‐perovskites ([H2DABCO](H4IO6)2·2H2O, named TDPI‐0) and perovskitoid energetic materials (PEMs) ([H2DABCO][M(IO4)3]; DABCO=1,4‐Diazabicyclo[2.2.2]octane, M=Na+, K+, and NH4+ for TDPI‐1, ‐2, and ‐4, respectively). The tolerance factor is first introduced to guide the design of perovskitoid energetic materials (PEMs). In conjunction with [H2DABCO](ClO4)2·H2O (DAP‐0) and [H2DABCO][M(ClO4)3] (M=Na+, K+, and NH4+ for DAP‐1, ‐2, and ‐4), the physiochemical properties of the two series are investigated between PEMs and non‐perovskites (TDPI‐0 and DAP‐0). The experimental results show that PEMs have great advantages in improving the thermal stability, detonation performance, initiation capability, and regulating sensitivity. The influence of X‐site replacement is illustrated by hard–soft‐acid–base (HSAB) theory. Especially, TDPIs possess much stronger initiation capability than DAPs, which indicates that periodate salts are in favor of deflagration‐to‐detonation transition. Therefore, PEMs provide a simple and feasible method for designing advanced high energy materials with adjustable properties.