Two Al-MOFs, i.e., MIL-53 (Al) and (NH2)-MIL-53 (Al) have been synthesized using aluminium nitrate as metal ligands and 1,4 benzene dicarboxylic acid, amino 1,4 benzene dicarboxylic acid as organic linkers in aqueous medium at room temperature, respectively. Both Al-MOFs have been confirmed through different microscopy and spectroscopy tools. Afterwards, the optical properties of Al-MOFs have been confirmed in polar and non-polar solvents using photoluminescence spectroscopy. Finally, both Al-MOFs have been explored for optical nitrobenzene (NB) sensing. Interestingly, we have found excellent optical ability of NH2-MIL-53 (Al) over MIL-53 (Al) due to structural π–π* transitions. The photo-induced electron transfer mechanism has been found during the MOF–analyte interaction. Importantly, we confirmed that NH2-MIL-53 (Al) is an excellent sensing material for NB with a 0.28 ppb limit of detection over MIL-53 (Al).