Syntheses and cation-binding abilities of a series of Calix[4]arene-crown ethers have been investigated. The syntheses of 1,3-dihydroxy-p-tert-butylcalix[4]arene-crown ethers and calix[4]arene-monocrown ethers bearing alkyl chains have been described. Solvent extraction of alkali and heavy metal picrates between water and dichloromethane has been carried out in order to reveal the effects of aromatic ring, size of crown ether ring, and substituents at the lower rim with cone conformation on their cation-binding ability. The extractability of metal picrates has been measured and compared with those of calix[4]arene derivatives and benzo-type crown ethers. The results showed that the introduction of crown ether ring (crown-4,5,6) increased the cation-binding ability compared with calix[4]arene derivatives. The cation-selectivity (potassium, silver, or thallium) has also been obtained by the change of ring size and branched aliphatic chains (n-propyl or isopropyl chain). Their cation-binding ability, cation selectivity, and aspects of the coordination chemistry in solvent extraction have been discussed in terms of crown ether ring size, symmetry, and conformation of the calix[4]arene-crown ethers.