Metal-organic frameworks (MOFs) as a new generation of functional molecular materials, have broad application prospects in enantioselective catalysis and chiral separation areas due to their unusual properties, such as high surface area, rich topologies, permanent microporous, availability of outer-surface modification and so on. A single-handed helical three-dimensional metal-organic framework material [{Cu(sala)}n] (H2sala=N-(2-hydroxybenzyl)-L-alanine) was incorporated with peramylated β-cyclodextrin for the preparation of novel capillary gas chromatography stationary phase. To investigate whether the use of a chiral MOF can enhance enantioseparation on peramylated β-cyclodextrin, three chiral columns were fabricated using different stationary phases for comparison, including column A ([{Cu (sala)}n]), column B (peramylated β-cyclodextrin) and column C ([{Cu(sala)}n]+peramylated β-cyclodextrin). The results of comparing the resolving abilities of the three columns for the same chiral compounds demonstrated that column C showed better enantioselectivity and higher resolution. The use of MOF [{Cu(sala)}n] can improve enantioseparation on peramylated β-cyclodextrin.