In this article, a new off-mode fluorescent platform based on the metal-organic framework (MOF) is introduced as a highly selective and rapid chemical sensor for the detection of As(III) in water and wastewater samples. A typical Fe-BTC (BTC = 1,3,5-benzenetricarboxylate or trimesic acid) MOF was used as a porous template for loading gold nanoparticles (AuNPs@Fe-BTC MOF). The physicochemical properties of AuNPs@Fe-BTC MOF were characterized by Fourier-transform infrared spectroscopy (FT-IR), Field emission scanning electron microscopy (FESEM), Energy-dispersive X-ray spectroscopy (EAX), element mapping (MAP) and X-ray diffraction (XRD) analysis. This sensing method for As(III) ions is based on the fact that the fluorescence intensity of AuNPs@Fe-BTC MOF sensor decreases in proportion to the increase in As(III) concentration. The main effective factors on the performance of the sensor signal such as MOF dosage, sonication time, pH and reaction time were optimized. Under optimized conditions, the calibration graph was linear in the concentration range of 0.5–380 ng mL⁻¹ of As(III) and the limit of detection was 0.2 ng mL⁻¹. The proposed method was successfully validated by addition/recovery experiments by the determination of As(III) in four river water and two wastewater effluent samples.