Rapidly synergistic cloud point extraction (RS-CPE) was coupled with tungsten coil electrothermal atomic absorption spectroscopy (W-coil ET-AAS) for the first time in this work. The extraction procedure using RS-CPE was very simple and accomplished in 1 min. The novel preconcentration technique was coupled with W-coil ET-AAS for nickel detection. The relevant factors and instrumental conditions that influence the RS-CPE were studied systematically. Under the optimal conditions, the limit of detection (LOD) was 0.2 μg L⁻¹, with a sensitivity enhancement factor (EF) of 45. The relative standard deviation (RSD) for seven replicate measurements of 20 μg L⁻¹ of nickel was 4.8%. The developed coupling was applied to the analysis of real and certified water samples with satisfactory results. In order to validate its application in field analysis, a number of environmental samples were studied.