The primary hydroxy groups of head‐tail and head‐head bis(sugar)‐based crown ethers (1 and 3, respectively) were acylated by (EtO)2P(O)Cl and Ph2P(O)Cl in a selective manner. Cation binding ability of the bis‐phosphorylated and phosphinylated macrocycles (2 and 4) was evaluated by the picrate extraction method. Introduction of the P‐moieties led to increase of the extraction ability without significant selectivity. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:267–270, 2000