In the presence of Al-pillared bentonite with good sorption capacity, nanoscale zero-valent iron supported on Al-pillared bentonite (NZVI/Al-PILC) was prepared with NaBH4 and FeSO4 aqueous solution. The structure of NZVI/Al-PILC was characterized by X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET). The effects of pH values and initial chromium (VI) concentrations on its removal rate by NZVI/Al-PILC were investigated, and were compared with those of unsupported nanoscale zero-valent iron (NZVI) containing the same iron mount of NZVI/Al-PILC. The results indicate that in the same experimental condition, the chromium (VI) removal by NZVI/Al-PILC reached 100% after 120 min. The removal is not only much higher than that (63.0%) of the NZVI containing same iron mount, but also superior to the sum of removal (75.4%) by NZVI containing the same iron amount and the Al-pillared bentonite containing the same clay amount with NZVI/Al-PILC.