A very simple and sensitive adsorptive anodic stripping voltammetric method was developed for determination of antimony(III) on a glassy carbon electrode (GCE), using rivastigmine (RIV) as the chemical receptor. No study on the usage of antimony(III) for metal determination as a modifier/complexing agent/chemical receptor was found in the literature review. The proposed method is based on the accumulation of the Sb–RIV complex on GCE under stirring conditions using optimized accumulation potential and time following the recording of a differential pulse (DP) voltammogram in anodic direction. The calibration graph consisted of two linear segments of 5.0×10−4–0.5μM (ip(μA)=7.45CSb(III)(μM)+0.05, R2=0.9974) and 0.5–2.5μM (ip(μA)=10.45CSb(III)(μM)−0.76, R2=0.9959) with a detection limit of 7.1×10−11molL−1. The RSD (n=5, intra-day) for 1.0×10−6molL−1 Sb(III) and 5.0×10−7molL−1 Sb(III) were calculated as 1.53% and 2.62%, respectively. Inter-day precision (n=5) was also calculated as 2.16% for 1.0×10−6molL−1 Sb(III), indicating that the proposed method has good precision. The spiked water sample analyses were evaluated using the described method and a good recovery of Sb(III) was obtained with results in the range from 95.0% to 97.6%.