The analytical opportunities of non-typical systems for extraction considerably grow with addition in a water phase anionic ligands: halogenides, pseudohalogenides as appropriate salts of alkaline metals. The complex of techniques of determination both hard and soft metal cations, and also phenol, determined particles, based on extraction, in systems with a unique liquid component # water, is developed. As water serves the unique liquid solvent of phase-splitting system, such systems meet the requirements of #green# analytical chemistry. Reactants are solid powder and accessible substances. The optical and electrochemical properties of an organic phase of systems allow to register analytical signals of microelements on absorption and limiting diffusion current, that is to realize ending analytical procedure by the optical or electrochemical method of the polyelement analysis. In a case of voltammetry for registration of peaks limiting diffusion current microelements the microliter quantities of organic phase

are required.