This article focuses in the development of high thermal resistant, fireproof, and durable expanded perlite based lightweight aggregate composites with a good balance between the thermal and mechanical properties. The thermal insulation boards were prepared with expanded perlite, coal fly ash, and aluminum dihydrogen phosphate by the process of mixing, molding, demolding, and calcinations, and surface treatment with an organic silicon abhorred agent. Coal fly ash is used to obtain an appropriate mechanical strength. The mechanical strength, thermal properties, and porosity structure of the designed composites are studied. The aggregate composites are well satisfied the Chinese expanded perlite insulation standard GB/T 10303‐2001, can be used as insulation materials, with the bulk densities 253 kg m−3–305 kg m−3, the compressive strengths 0.428 MPa–0.462 MPa, and the heat conductivities 0.073 W m−1 K−1–0.082 W m−1 K−1, and could be applied in high‐rise building instead of normally used organic insulation materials. © 2017 American Institute of Chemical Engineers Environ Prog, 37: 1319–1326, 2018