Herein we describe an efficient, simple, and precise micelle-mediated microextraction strategy based on the aggregation behavior of surface-active ionic liquids (SAILs) for the preconcentration and determination of cobalt ions in pharmaceutical preparations. Unlike the commonly used hydrophobic ionic liquids in IL-based microextraction methods, a water-soluble surface-active ionic liquid [1-hexadecyl 3-methylimidazolium chloride (C16MeImCl)] was used. A modified cloud point extraction (CPE) procedure based on the C16MeImCl-Triton X-114 mixed micellar system was proposed as an efficient extracting phase. A comparison of the analytical features of the extraction process with and without SAILs revealed the benefits of the proposed method. Advantages such as a wider linear range, lower detection limit, higher reproducibility, and improved extraction efficiency highlighted the proposed method over the conventional CPE method. These attractive specifications are due to the higher extraction efficiencies achieved in the presence of the SAIL and its favorable effects at the phase separation stage. Various parameters affecting the extraction efficiency were optimized by univariate and multivariate (Box-Behnken design) approaches. The calibration curve was obtained in the optimal experimental conditions with a linear range from 0.01 to 5.5 mg L-1 of cobalt ion concentration (R = 0.9992) and a detection limit of about 0.005 mg L-1. The RSD% for 10 replicate determinations of 1.0 mg L-1 Co was 0.9%. The proposed method was successfully applied to determine cobalt ions in vitamin B12 ampoules and tablets.