A series of N-cycloalkylprolinamides have been designed and synthesized from achiral cycloalkylamines in a facile manner. They promoted high stereoselectivity in the cross-aldol reaction. N-cyclopropylprolinamide performed best with a smallest carbocyclic ring, and the anti-aldol products could be obtained with up to 99:1 anti/syn and 99% ee. Carbocyclic ring was found to play a significant role in the formation of the aldol products. This simple catalyst can be efficiently used in large-scale reactions with the enantioselectivity being maintained at the same level, which offers great possibility for applications in industry.