Volatile organic compounds (VOCs) pose significant risks to environmental quality and human health. To enhance adsorption performance of adsorbents for VOCs, further improvement of the unsaturated metal centers becomes a key factor based on the principle that metal ions can be replaced in metal organic frameworks (MOFs). Here, a one-step solvothermal synthesis system was utilized to dope abundant, cost-effective, and environment friendly Al³⁺ ions into MIL-101(Cr) for preparing Al-MIL-101(Cr). Morphologies and structures of MIL-101(Cr) and Al-MIL-101(Cr) samples, alongside the static adsorption performance for toluene, n-hexane, oil and p-xylene, were analyzed. Static adsorption capacities of toluene, n-hexane, oil, and p-xylene of MIL-101(Cr) were 0.676, 0.621, 0.451 and 0.812 g·g^-1, respectively. When Al³⁺ doping amount reached 0.75 mmol, Al-0.75-MIL-101(Cr) displayed maximum VOCs adsorption capacities (0.911 g·g^-1 for toluene, 0.755 g·g^-1 for n-hexane, 0.713 g·g^-1 for oil, and 0.875 g·g^-1 for p-xylene). The dynamic toluene adsorption behavior was assessed through single-component breakthrough curves. Both dynamic and static adsorption results demonstrate that Al-MIL-101(Cr) possesses excellent VOCs removal capabilities, which are attributed to the extensive specific surface area and augmented unsaturated metal sites.