The importance of alkyl chain length and concentration of quaternary ammonium surfactants (QAS) in the micellar catalysis of cross aldol reaction was investigated. The NaOH-micellar system catalyzed aldol reaction of benzaldehyde and cyclohexanone to alpha,alpha'-dibenzylidene cyclohexanone (di condensation/desired product) over mono condensation product was used as model reaction for this study. The C(16)QAS micellar system (QAS with n-hexadecyl group) gave highest cyclohexanone conversion (90%) to desired product (82%) showing that C(16)QAS micellar system possesses optimum properties and/or microenvironment for this reaction. Furthermore, the micellar system with high surfactant concentration (C(16)QAS; >150 mM) made the reaction faster giving >99% conversion to selectively desired product (>99%) within 30 min The large interface created by C(16)QAS micelles in the aqueous medium at high surfactant concentration makes the reaction faster by facilitating the interaction of hydrophobic reactants and water soluble catalyst (OH- ions). The activation of benzaldehyde molecules, their localization preferably near the interface and stabilization of enolate ions (reactive intermediates) by micellar system at high surfactant concentration were observed to be promoting the cross reaction selectively to the desired product. (C) 2014 Elsevier B.V. All rights reserved.