Unithiol, as a biologically active ligand that forms stable complexes with metals, is of significant interest and requires systematic research when designing efficient medicinal agents. The accelerated “green” synthesis of a tungsten complex with unithiol as a ligand is carried out using two methods: ultrasonic and microwave. The precursors to this reaction are an extract of Picea pungens Engelm. spruce needles as a natural source of presumably bioactive unithiol and sodium tungstate; the reaction duration is 15 min. X-ray absorption spectra (XANES) near the L3 edge of tungsten absorption for a tungsten–unithiol complex are obtained and qualitatively analyzed for the first time.