Abstract A cloud point extraction procedure for the preconcentration of Pb2+ in various samples following complexation with 2,2-(1E,1′E)-1,1′-(2,2′-azanediylbis(ethane-2,1-diyl)bis(azan-1-yl-1-ylidene)) bis(ethan-1-yl-1-ylidene)diphenol in Triton X-114 after centrifugation is reported. A 0.5 mL portion of methanol acidified with 1.0 M HNO3 was added to the surfactant-rich phase prior to analysis by flame atomic absorption spectrometry. The influence of analytical parameters—including pH, concentrations of ligand, Triton X-114, and HNO3, bath temperature, heating time, and centrifugation rate and time—were optimized, and the effect of the matrix ions on the recovery of Pb2+ was investigated. An LOD of 1.9 ng/mL along with a preconcentration factor of 50 with RSD of 1.0% for Pb2+ were achieved. The proposed procedure was applied to the analysis of various real samples.