Abstract:5,11,17,23,29,35-hexacarboxy-37,38,39,40,41,42-hexa-methoxy-hydroxamic calyx[6]arene (HHMHC) was synthesized by modifying p-hydroxybenzoic acid, and characterized by IR. The effects of pH, Cu2+ and Ni2+ initial concentration, extraction time and temperature on the calixarenes extraction behavior of Cu2+ and Ni2+ were investigated. The results showed that the maximum extraction were observed under the experiment conditions of 30℃ with a contact time of 30min, a pH of 6.0(Cu2+), 5.0(Ni2+), when the initial concentration of Cu2+ and Ni2+ was 5mg/L. The extration of Cu(II) and Ni(II) onto HHMHC had a close agreement with the pseudo-second-order model (R2>0.99) and the Freundlich model (R2>0.999). In the extraction process, the negative values of Gibbs free energy (ΔG0) revealed this extraction was spontaneous. Meanwhile, the value of enthalpy(ΔH0) was negative, indicating that the extraction reaction was exothermic progress. Based on the analysis of IR spectra and the effect of pH on the extraction distribution ratio (D), it was found that the extraction mechanism of Cu2+ and Ni2+ with HHMHC not only followed the ion exchange mechanism, but also included the coordination effect, on which the functional group -CONHOH played an important role.