A relatively rapid and precise method is presented for the determination of lead in aqueous matrix. The method consists of analyte quantitation using the liquid electrode plasma-optical emission spectrometry (LEP-OES) coupled with selective separation/preconcentration by solid-phase extraction (SPE). The impact of operating variables on the retention of lead in SPEs such as pH, flow rate of the sample solution; type, volume, flow rate of the eluent; and matrix effects were investigated. Selective SPE-separation/preconcentration minimized the interfering effect due to manganese in solution and limitations in lead-detection in low-concentration samples by LEP-OES. The LEP-OES operating parameters such as the electrical conductivity of sample solution; applied voltage; on-time, off-time, pulse count for applied voltage; number of measurements; and matrix effects have also been optimized to obtain a distinct peak for the lead at lambda(max) = 405.8 nm. The limit of detection (3 sigma) and the limit of quantification (10 sigma) for lead determination using the technique were found as 1.9 and 6.5 ng mL(-1), respectively. The precision, as relative standard deviation, was lower than 5% at 0.1 mu g mL(-1) Pb, and the preconcentration factor was found to be 187. The proposed method was applied to the analysis of lead contents in the natural aqueous matrix (recovery rate: > 95%). The method accuracy was verified using certified reference material of wastewaters: SPS-WW1 and ERM-CA713. The results from LEP-OES were in good agreement with inductively coupled plasma optical emission spectrometry measurements of the same samples. The application of the method is rapid (<= 5 min, without preconcentration) with a reliable detection limit at trace levels.