Alkyl-15-crown-5 and alkyl-12-crown-4 were prepared via polyethylene glycol β-haloalkyl ethers in two steps from terminal olefins, and their complexing ability with cations of alkali and alkaline earth metals was measured by using 1 H NMR; it was found to be almost identified with that of the corresponding unsubstituted crown ether. A new type of alkyl crown ether with a chloro substituent could also be synthesized according to this method.