Efficient separation of radioactive cesium ions (Cs+) from complicated aqueous environmental media has attracted considerable interest, especially seawater. Ammonium molybdophosphate (AMP) is regarded as a promising adsorbent for Cs+, but its fine powder dramatically inhibits the potential for practical applications. Herein, graphene oxide (GO) was utilized as a support for the in-situ growth of AMP, and after vacuum filtration, GO/AMP composite membrane was successfully fabricated. It was found that the GO/AMP membrane exhibited excellent adsorptive filtration performance (47.3 L m−2h−1 bar−1 water flux and 99.2 % rejection for Cs+ with 20 ppm initial concentration, 30 mL feed solution). Influent pH and coexisting metallic ions had scarcely effects on Cs+ rejection. Over five cycles, the water permeability and Cs+ rejection remained essentially unchanged. Moreover, the decontamination of Cs+ from real seawater was demonstrated with the rejection ratio as high as 87.4 % and a relatively inhibitory flux of 14 L m−2h−1 bar−1. Based on FT-IR, XPS, and EXAFS analyzes, the rejection of Cs+ was mainly ascribed to the exchange of NH4+ in AMP with Cs+ in solution, and an inner-sphere coordination of Cs+ rather than a weak outer-sphere interaction between hydrated Cs+ ions and adsorbent occurred.