A series of tertiary amine and siloxane crosslinked composite anion exchange membranes were prepared by incorporating 2‐(3,4‐epoxycyclohexyl) ethyltrimethoxysilane (EHTMS) and N,N,N′,N′‐Tetramethyl‐1,6‐hexanediamine (TMHDA) into N‐Methyldiethanolamine (MDEA)‐functionalized poly (2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) backbone via sol‐gel process. The resultant membranes named as AEM‐X (X = 1, 2, 3, 4), which own a three‐dimensional (3D) cross‐linking structure, exhibit superior swelling resistance, mechanical properties, even the thermal stability is up to 220°C. Compared with AEM‐1 (contains no crosslinker), the swelling ratio of AEM‐2 obviously decreases by 10.2% at 80°C, while the OH− conductivity of AEM‐2 has a merely 1.9% decline (20.6 mS cm−1) at 80°C and can maintain 67% of its initial value in a 2 M aqueous NaOH at 80°C for 240 h. The simultaneous introduction of inorganic siloxane and organic linear crosslinker provides a new idea for the preparation of anion exchange membranes with largely improvement in dimensional stability and alkali resistance while the ionic conductivity is kept at comparatively high level.