A new macrocyclic calix[4]arene-bis[(4-methyl-1,2-phenylene)-crown-6] (CalixBisMePhC) was synthesized. An extraction study of Cs(I), Na(I), K(I), Rb(I), Sr(II), Ba(II), Pd(II), and Ru(III) with CalixBisMePhC/CHCl3 was investigated by examining the effects of contact time, HNO3 concentration, and temperature. The results showed that due to the effective molecular recognition, CalixBisMePhC/CHCl3 had excellent extraction ability and high selectivity for Cs(I) over the tested metals except Rb(I). The maximum distribution ratio for Cs(I) was found at the HNO3 concentration of 4.4 mol.kg(-1). The composition of the extracted species of Cs(I) was determined to be CsNO3 center dot 0.5CalixBisMePhC center dot 0.5HNO(3) by a slope method. Some valuable parameters for the Cs(I) extraction were obtained. The results demonstrated that the CalixBisMePhC/CHCl3 extraction system is promising to partition Cs(I) from highly level liquid waste.