The chromatographic behaviour of 60-a-D-glucosyl-, 6-0-a-maltosyl and 6-0-a-maltotriosyl derivatives of a-, /?-and y-cyclodextrin (CD) and of 66"-di-O-a-D-glucosyl-B-CD on three kinds of high-performance liquid chromatographic (HPLC) columns and four kinds of thin-layer chromatographic (TLC) plates was investigated. The order of elution of these branched CDs on a Hibar LiChrosorb NH2 column with acetonitrile-water followed the order of increasing molecular size. On the other hand, their elution profiles on a Hibar LiChrosorb RP-18 column with methanol-water and on an Asahipak GS-320 column with water were different from that on the NHz-bonded silica, that is, the member of the y-CD series eluted first among the three CD derivatives having the same side-chains, then the a-CD derivative and the @CD derivative considerably behind that. The two systems differed from one another in the elution sequence of the members in each series. TLC analyses were performed on silica gel 60 TLC plates and HPTLC plates with 1-propanolethyl acetate-water-25% ammonia solution, on NH2 HPTLC plates with acetonitrilewater and on Si 50000 HPTLC plates with 1-butanol-pyridine-water, and their utility as a more convenient method than HPLC for the analysis of CDs was recognized. The analysis on the NH2 HPTLC plate may be used as a pilot for HPLC analysis on NHz-bonded silica.