A novel pillar [5] arene-based heteroditopic receptor for ion pair recognition of alkylammonium salts with different alkyl chain lengths and different counterions was prepared, which showed the best association constant enhancement (71times) to n-BuNH3+ Cl− compared with monotopic receptor 1, 4-dimethoxypillar [5] arene over corresponding Br− and CF3COO− salts in chloroform.