A simple and efficient ionic liquid-based ligandless microextraction method has been developed for preconcentration of cadmium ions (Cd2+) as a step prior to its determination by flame atomic absorption spectrometry (FAAS) with a micro-sample introduction system. In this approach, the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate [C(4)mim][PF6] and ethanol were used as extractant and dispersive solvents to preconcentrate the Cd2+ in different waters, acid digested scalp hair, and nail samples. Some analytical parameters influencing the extraction efficiency of Cd2+ and its subsequent determination, including pH, IL volume, dispersant solvent volume, sample volume, temperature, incubation time, and matrix effect, were optimized. Under optimal conditions, the limit of detection (LOD), limit of quantification (LOQ), and enhancement factor (EF) were 0.4g L-1, 1.3g L-1, and 50, respectively. The relative standard deviation (RSD) of 100gL(-1) Cd2+ was 4.3% (n = 6). The validity of the proposed method was checked by determining Cd2+ in certified reference material (TM-25.3 fortified water) and standard addition; the results showed sufficient recovery (>98%) of Cd2+ within the certified value. The method was applied for preconcentration and determination of cadmium in waters and biological samples.