The synthesis and self-assembled monolayer (SAM) formation of three conformational isomers of p-tert-butylcalix [4]crown-6 derivatives 3a−3c and one p-tert-butylcalix [4]arene derivative (3d) are reported. The SAMs of these compounds were prepared and characterized by electrochemistry, reflection-absorption infrared spectroscopy (RAIRS) and contactangle measurements. The recognition properties of these