AbstractThis study is mainly focused on the crystalline structure and mechanical properties of autoclaved aerated concrete (AAC) without losing any other specific performances such as low bulk density and good thermal insulation capacity. For this purpose, colemanite (C) was added in a proportion of 0.3, 1, 3, 10, 15, 20, and 30% by weight to standard G2/350 receipt during raw material mixing process. After mixing, mud prepared with the suitable amount of starting materials with water was slipping into the laboratory scale metal moulds. Moulded samples were cured under the condition of 55% humidity and 50–55°C for 4 h and sent to autoclave line. Cut‐sized samples were left under the 12 bars pressure for 5 h. Density (Kg/m3), lambda values (W/mK), and compressive strength (MPa) of the samples have been measured. Selected samples that have the highest mechanical strength were examined mineralogically (XRD) and microstructurally by scanning electron mircoscope (SEM). The results show that boron atoms from calcined colemanite (CC) diffused into the tobermorite crystalline structure and remained as an interstitial atom in this structure. Thus, mechanical performance of samples with CC increased more than double time according to the standard G2/350 recipe.