Fe-based metal-organic framework MIL-88A microrods were synthesized by hydrothermal method, which were used to adsorb As(V) in water for the first time. The experimental results indicated that MIL-88A has a very fast adsorption rate towards arsenic in water. The kinetic and isothermal data for arsenic removal were better fitted to the pseudo-second-order kinetic model and Langmuir model, respectively, implying a chemical and monolayer adsorption for As(V) on MIL-88A microrods. Two rate-controlling processes during adsorption were revealed by the intraparticle diffusion model. The maximum adsorption capacity of MIL-88A reached 145 mg g−1, higher than those of Fe-based MIL adsorbents reported previously, which probably originates from its unique microstructure with abundant OH−groups and an unusual large swelling towards water. These show that Fe-based MIL-88A is a good candidate for arsenic removal.