The liquid membrane transport of Na+ ions by p-tert-butylcalix[6]arene and that of K+ ions by p-tert-butylcalix[8]arene were investigated by means of a bubbling pseudo-emulsion liquid membrane system. This system represents a proton-coupled transport with a flow of protons in the opposite direction. The driving force for the transport is the pH gradient between the source and receiving phases. When the pH difference between the two phases is sufficient, the carriers calix[6]arene(or calix[8]arene) can successfully transport Na+ (or K+) ions from the source phase with a lower Na+ (or K+) concentration into the receiving phase with a higher Na+ (or K+) concentration, like a Na+ (or K+) ion pump.