Monolayers of pure enantiomers and the racemic mixture of the amphiphilic N-dodecylgluconamide were investigated at the air-water interface using Brewster angle microscopy and surface pressure measurements. A striking chiral discrimination is demonstrated comparing the pure enantiomeric forms and the racemic mixtures. The monolayer morphology obtained on compression was visualized and studied by Brewster angle microscopy. The enantiomeric N-dodecylgluconamides form regular ramified growth pattern of high-stability in a shape characteristic for dendritic crystallization, while the racemic mixtures show isotropical solidification. The chiral discrimination effect is supported by differences in the surface pressure isotherms and the constant surface pressure relaxations of the pure enantiomeric forms and the racemic mixtures. The dendritic crystallization found experimentally is discussed in respect of the molecular organization at the air-water interface.