3-O-( p-Allyloxybenzoyl)heptakis(2,6-di-O-methyl)-β-cyclodextrin, which was used for preparation of permethylated 3-O-( p-allyloxybenzoyl)-β-cyclodextrin ( 4), was produced in a 15% yield by a monoesterification of heptakis(2,6-di-O-methyl)-β-cyclodextrin. Heptakis[6-O-( tert.-butyl)dimethylsilyl]-β-cyclodextrin was regioselectively monoesterified with p-allyloxybenzoyl chloride or p-( tert.-butyl)benzoyl chloride to yield 2-O-( p-allyloxybenzoyl)heptakis[6-O-( tert.-butyl)dimethylsilyl]-β-cyclodextrin ( 6) or 2-O-[ p-( tert.-butyl)benzoyl]heptakis [6-O-( tert.-butyl)dimethylsilyl]-β-cyclodextrin ( 7). Compound 6 was acylated to give tridecaacetate 8, which was deprotected and methylated, to give 2 A-O-( p-allyloxybenzoyl)heptakis(3-O-acetyl-6-O-methyl)- 2 B,2 C,2 D,2 E,2 F,2 G-hexa-O-acetyl-β-cyclodextrin ( 10). Both 6 and 7 were methylated, following by deprotection and methylation (on the 6-position), to give permethylated 2 A-O-( p-allyloxybenzoyl)-β-cyclodextrin ( 15) and permethylated 2 A-O-[ p-( tert.-butyl)benzoyl]-β-cyclodextrin ( 16), respectively. Then, 16 was treated with lithium aluminum hydride to form monoalcohol, which was transformed into permethylated 2 A-O-( p-allyloxybenzyl)-β-cyclodextrin ( 18) by a nucleophilic substitution reaction. Four new permethyl- or per(methyl/acetyl)-substituted β-cyclodextrin-bound methylpolysiloxanes were prepared by a hydrosilylation reaction of the monoalkenyl-substituted β-cyclodextrin derivatives 4, 10, 15 and 18 with a specially prepared hydromethylpolysiloxane. The polymeric phases provide excellent enantiomeric separations of a variety of chiral solutes in open tubular column supercritical fluid chromatography and gas chromatography.