Herein, switchable hydrophilicity solvent (SHS) was used as a synergistic reagent in the cloud point extraction (CPE) protocol to increase the procedure’s efficiency and sensitivity. At room temperature, the CPE-SHS method was created for the fast and accurate extraction of antimony from a variety of drinks. Hydride generation atomic absorption spectroscopy (HGAAS) was used to antimony detection in various samples following the CPE-SHS protocol. The N,N-dimethylamine (DMA), TritonX-100, and p-tert-butyl-tetrakis[(diethylamide)methoxy]tetrathiacalix[4]arene (BTDMTA) were used as a SHS, surfactant, and chelation reagent, respectively. This procedure’s criteria for validation have been identified, including linearity (0.01–700 µg/L), accuracy, precision, limit of detection (LOD = 0.007 µg/L), limit of quantification (LOQ = 0.023 µg/L), enhancement factor (EF = 160), and matrix influence. This approach was validated using certified reference material. The environmentally friendly practices of this method were assessed using recent tools like Complex Modified GAPI (ComplexMoGAPI) software, Analytical GREEnness Calculator (AGREE) software, Blue Applicability Grade Index (BAGI) software, and Sample Preparation Metric of Sustainability (SPMS) program.