This paper reports on the synthesis and surface immobilization of a 40-membered chiral salen macrocycle via a surface reaction between its hydroxyl-terminated branches and a carboxy-functionalized platform using N,N'-dicyclohexylcarbodiimide (DCC) as activating molecule of the carboxylic group of 11-mercaptoundecanoic acid, SAM. The peculiarity of this surface reaction at the carboxy-terminated platform is that a multiple site esterification is obtained, as indicated by time-of-flight secondary ion mass spectrometry measurements. Copyright (C) 2010 John Wiley & Sons, Ltd.