A novel konjac glucomannan (KGM)‐acrylic acid‐diatomite composite (KGAD) was synthesized by the solution polymerization of partially neutralized acrylic acid (AA) on to KGM and diatomite (DT), using potassium persulfate as a free radical initiator, in the presence of Trimethylolpropane Trimethacrylate (TPTA) as a crosslinking agent. The structure and morphology of KGAD were characterized by using FT‐infrared, X‐ray diffraction, scanning electron microscopy. Besides, the thermal stability as well as the salt absorption of the composites was investigated by the thermogravimetric analysis and the swelling rate test, respectively. The results showed that the interactions between KGM‐AA (KGA0) and DT could be generated through hydrogen bond formation. Besides, the crystal of composites became rules and grew well with the addition of DT. It was also found that the appropriate amount of DT could be dispersed uniformly with a single crystal state in the matrix of KGA0 while excessive DT caused aggregation, inducing an irregular distribution in the matrix. In addition, the thermal stability of KGAD was improved based on the introduction of DT into the polymer network. POLYM. COMPOS., 37:3384–3390, 2016. © 2015 Society of Plastics Engineers