Hierarchically porous MIL-101(Cr) (H-MIL-101(Cr)) with meso/macro-pores was directly prepared via nanofusion progress by using butyric acid as a modulating agent. In the methyl orange (MO) adsorption experiments, H-MIL-101(Cr) showed a high adsorption capability of 369.8 mg g-1, which was 1.52-fold greater than that of pristine MIL-101(Cr) (P-MIL-101(Cr)). While in the oxidation reaction of indene and 1-dodecene tests, H-MIL-101(Cr) presented much higher catalytic efficiency, with turnover frequency (TOF) values of 0.7242 mmol g-1 min-1 and 0.1492 mmol g-1 min-1, respectively, which were 28% and 34% greater than that in the case of P-MIL-101(Cr). Thus, compared with P-MIL-101(Cr), H-MIL-101(Cr) exhibited better removal efficiency and higher levels of activity in the oxidation reactions of indene and 1-dodecene. The unique structure of H-MIL-101(Cr) also contributed to its superior performance in these processes.