The bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex-272) and sodium diethyl- dithiocarbamate (NaDDC) ligands were used to extract of metal ions ($Cd^{2+},;Co^{2+},;Cu^{2+},;Pb^{2+},;Zn^{2+}$) in supercritical $CO_2$. Experiments showed a strong synergistic effect and better extraction efficiency if the two ligands were used together. In-situ UV-visible observation indicates that NaDDC in the water^{ercritical $CO_2$<} started to decompose slowly. The synergistic effect seems to come from the deprotonation of the organophosphorus ligand by amines from the decomposed NaDDC. The enhancing role of amines was confirmed using the mixture of Cyanex-272 and diethylamine(DEA) in the metal extraction.