In order to protect human health from the adverse impacts of acrylamide and acetone, simple analytical processes are required to detect low concentrations of acrylamide and acetone. Dual functional garlic-capped silver nanoparticles (G-Ag NPs) have been used as fluorescent sensors for acrylamide and acetone. This technique depends on the quenching of the photoluminescence (PL) intensity of G-Ag NPs with the interaction of either acrylamide or acetone. This fluorescent probe presented high selectivity toward acrylamide with a wide linear response of 0.01–6 mM with a limit of detection (LOD) of 2.9 μM. Moreover, this probe also acted as a selective and sensitive fluorescent sensor for the detection of acetone in the range of 0.1–17 mM with LOD of 55 μM. The applicability of G-Ag NPs as a proposed sensor for acrylamide was evaluated using a potato chips sample with a recovery percentage of 102.4%. Acetone concentration is also quantified in human urine samples and the recoveries ranged from 98.8 to 101.7%. Repeatability and reproducibility studies for acrylamide and acetone offered relative standard deviation (RSD) of 0.9% and 1.5%, and 0.77% and 1.1%, respectively.