The confinement of small amounts of benzene in InOF-1 (Bz@InOF-1) shows a contradictory behavior in the capture of CO2 and SO2. While the capture of CO2 is increased 1.6 times, compared to the pristine material, the capture of SO2 shows a considerable decrease. To elucidate these behaviors, the interactions of CO2 and SO2 with Bz@InOF-1 were studied by DFT periodical calculations postulating a plausible explanation: (a) in the case of benzene and CO2, these molecules do not compete for the preferential adsorption sites within InOF-1, providing a cooperative CO2 capture enhancement and (b) benzene and SO2 strongly compete for these preferential adsorption sites inside the MOF material, reducing the total SO2 capture.