The goethite (α-FeOOH) nanoparticles were wrapped on the reduced graphene oxide (rGO) to synthesize the α-FeOOH/rGO nanocomposites. The nanocomposites (NCs) were initially examined for their optical, structural, and morphological properties. The XRD data obtained the crystallite size of the α-FeOOH, showed that the average crystal size for pristine α-FeOOH and α-FeOOH/rGO nanocomposites were about 85 and 90 nm, respectively. The transmission electron microscope confirmed the nanoparticles (NPs) were evenly distributed throughout the reduced graphene oxide sheets. The nanocomposites improved glassy carbon electrodes (GCE), making them efficient sensors for detecting the arsenic(III) (As+3) in a pH 5 phosphate buffer solution with an Ag/AgCl reference electrode. The detection limit for As+3 was 0.07 μgL−1 and the resulting sensitivity was 0.39 μA−1 μgL−1 in the linear dynamic range of 0.1–10 μgL−1. The α-FeOOH/rGO/GCE was more sensitive than its original and showed a synergistic effect due to the influence of α-FeOOH on the properties of rGO. The α-FeOOH/rGO NCs-modified GCE electrode performed as a promising sensor, by separating the common interfering ions. Moreover, the modified electrode exhibited remarkable stability, repeatability, and potential real-time application towards the detection of arsenic(III). Additionally, the proposed approach has been successfully applied to the detection of As+3 in the real water sample.