A new pyridine heterocyclic beta-cyclodextrin derivative, heptakis[2,6-di-O-pentyl-3-O-(2-chloro-5-pyridyl)methyl]-beta-CD, was synthesized and explored as chiral stationary phase in capillary gas chromatographic separation. Cyclopropane derivatives with two chiral centers including four configurational isomers or three chiral centers including eight configurational isomers were well separated, which indicated the new pyridyl P-CD derivative possessing excellent chiral selectivity for separation of complex compounds including multichiral centers.