MIL-100(Fe) was used for the first time in the catalytic transformation of hexose sugars into lactic acid (LA). The as-synthesized MIL-100(Fe) was systematically characterized, and its superior morphological and textural properties were demonstrated to contribute greatly to the pronounced catalytic performance in fructose-to-LA conversion (up to 32% yield), as compared with other catalysts like Cu-BTC and MIL-100(Cr). The effects of reaction conditions including temperature, reaction time, and substrate loading were explored. In addition, MIL-100(Fe) could be easily reused for 4 cycles with no evident decrease in catalytic activity.