The monitoring and precise determination of pesticides and pharmaceutical drugs and their residues have become increasingly important in the field of food safety and water contamination issues. Herein, a fluorescent aluminium MOF sensor (1) was developed for the selective recognition of neonicotinoid insecticide dinotefuran and anti‐Parkinson’s drug entacapone. Guest‐free MOF 1′ exhibited ultra‐fast response (< 5 s) and ultra‐low detection limits of 2.3 and 7.6 nM for dinotefuran and entacapone, which are lower than the previously reported MOF sensors. In the presence of other competitive analytes, great selectivity was achieved towards both analytes. The probe was recyclable up to five cycles. The sensing ability was explored towards entacapone in human serum, urine and dinotefuran in real soil, rice, honey samples, different fruits, vegetables, real water specimens and a wide range of pH media. A low‐cost, handy MOF‐based polymer thin‐film composite (1′@PVDF‐PVP) was developed for the on‐site detection of dinotefuran and entacapone. Mechanistic studies involving analytical techniques and theoretical calculations suggested that FRET and PET are the probable reasons for entacapone sensing whereas IFE is responsible for dinotefuran detection. The entire work presents a low cost, multi‐use photoluminescent sensor of entacapone and dinotefuran to address the environmental pollution.