Nanoscale MIL-101(Cr) metal–organic frameworks with giant pores, very large Brunauer–Emmett–Teller surface areas, and small dimensions in the nanoscale regime, were synthesized in high yields by an expanded graphite (EG)-templated hydrothermal strategy. Compared with a conventional hydrothermal method, the size of the MIL-101(Cr) crystals can be well controlled at nanoscale and the reaction time can be largely shortened from 8 to 2h using such an EG-templated hydrothermal method. The size of the MIL-101(Cr) crystals can be well controlled and the synthesis cycle can be largely shortened for many practical applications.