An analytical methodology based on coprecipitation-assisted coacervative extraction coupled to HPLC-UV was developed for determination of five organophosphorus pesticides (OPPs), including fenitrothion, guthion, parathion, methidathion, and chlorpyrifos, in water samples. It involves a green technique leading to an efficient and simple analytical methodology suitable for high-throughput analysis. Relevant physicochemical variables were studied and optimized on the analytical response of each OPP. Under optimized conditions, the resulting methodology was as follows: an aliquot of 9 mL of water sample was placed into a centrifuge tube and 0.5 mL sodium citrate 0.1 M, pH 4; 0.08 mL Al-2(SO4)(3) 0.1 M; and 0.7 mL SDS 0.1 M were added and homogenized. After centrifugation the supernatant was discarded. A 700 L aliquot of the coacervate-rich phase obtained was dissolved with 300 L of methanol and 20 L of the resulting solution was analyzed by HPLC-UV. The resulting LODs ranged within 0.7-2.5 ng/mL and the achieved RSD and recovery values were <8% (n = 3) and >81%, respectively. The proposed analytical methodology was successfully applied for the analysis of five OPPs in water samples for human consumption of different locations of Mendoza.