New chiral stationary bonded phases (CSPs) based on derivatized malto-oligosaccharides are reported. Chiral separations are reported for 3,5-dinitrobenzoyl-derivatized amines and amino acids as well as some 3,5-dinitrophenylcarbamoylated alcohols. These new CSPs incorporate a 1-(1-naphthyl)ethylcarbamate (NEC) moiety which introduces additional stereogenicity and provides a useful probe for investigating chiral recognition. The elution order, when known, was dependent upon the configuration of the NEC substituent; that is, the S enantiomers were retained longest on the S column and the R enantiomers were retained longest on the R column. Elution order from the RS column, when known, was the same as that observed for the S column. In most cases, retention correlated with bonded ligand concentration on the silica substrate. In general, the best enantioselectivities and resolution were obtained on the S column.