The aim of this work is to study the performances of isomeric α-, β-, and γ-FeOOH (goethite, akaganéite and lepidocrocite, including five samples named as Gth1 and Gth2, Aka1 and Aka2, and Lep, respectively) for removing hexavalent chromium (Cr(VI)) from aqueous solutions. The adsorption mechanisms were explored by kinetic and isothermal experiments. Adsorption efficiencies under the different pH values, anions, and the levels of adsorbate and adsorbent were also measured. Results showed that the Cr(VI) adsorption by isomeric FeOOH could be best described by pseudo-second-order kinetic model. The processes of Cr(VI) isothermal adsorption could be greatly fitted by the Langmuir and Freundlich equations with the high correlation coefficients of R2 (>0.92). Also, there were the optimum pH values of 3.0–8.0 for FeOOH to adsorb Cr(VI), and their adsorption capacities were tightly related with the active sites of adsorbents. Cr(VI) adsorptions by these adsorbents were easily influenced by H2PO4–, and then SO42–, while there were little effects by Cl–, CO32– and NO3–. These obtained results could provide a potentially theoretical evidence for isomeric FeOOH materials applied in the engineering treatment of the polluted chromate-rich waters.