The synthesis and complexing abilities of the two biscalix[4]arenes with ligating ester and ketone groups in the cone conformation have been performed and determined by extraction and extraction constants measurements. The cations studied were the alkali (Li+, Na+, K+, and Cs+) and transition (Ag+, Hg2+, Cu2+, Ni2+, Co2+, Cd2+) metals. It has been observed that ester derivative 7 shows a higher affinity toward transition metals than the alkali metal cations. By contrast, ketone derivative 8 extracts both alkali and transition metal cations effectively. Both of compounds 7 and 8 are better extractants than their monomeric analog 1.