In this paper we describe the solvent extraction behaviour of three calixarene-type cyclophanes towards trivalent lanthanides Ln3+(Ln = La, Nd, Eu, Er and Yb). By using p-tert-butylcalix/6/arene hexacarboxylic acid (LI), the lanthanides were extracted from the aqueous phase at pH 2 to 3.5 into chloroform according to a cation exchange mechanism as 1:2 metal:ligand complexes. The extractability is: Nd, Eu > La > Er > Yb. In the presence of excess Na+in the aqueous phase, this order was not changed but the lanthanides were extracted as 1 : 1 complexes at low extractant concentration and their extractability decreased.