Polyaniline (PANI) was modified onto 3D flower-like molybdenum disulfide (MoS2) to prepare a novel organic–inorganic hybrid material, [email protected]2. [email protected]2 was characterized by scanning and transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction and thermogravimetric analysis. The results indicate that PANI was modified onto MoS2. [email protected]2 was applied as an adsorbent to remove Cr(VI) from aqueous solutions, and the adsorption isotherms fit well to the Langmuir model; the maximum removal capacity of Cr(VI) by [email protected]2 was 526.3 and 623.2 mg/g at pH 3.0 and 1.5, respectively. [email protected]2 exhibited an enhanced removal capacity of Cr(VI) in comparison with bare MoS2 and other adsorbents. The adsorption of Cr(VI) on [email protected]2 might be attributed to the complexation between the amine and imine groups on the surface of [email protected]2 with Cr(VI). This study implies that the hybrid material [email protected]2 is a potential adsorbent for Cr(VI) removal from large volumes of aqueous solutions.