The composition of the volatile fraction of Egyptian Jasminum sambac (L.) Ait. (Family: Oleaceae) flowers picked in July (the climax of the flowering season), was studied using GC/MS. The flowers' concrete headspace (HS) volatiles had been analyzed by SPME (solid phase microextraction) and compared with those from the flowers' absolute. The main volatile constituents of the concrete HS and the absolute, respectively, were: benzyl acetate (23.7 and 14.2%), indole (13.1 and 13.4%), E-E-alpha-farnesene (15.9 and 13.1%), Z-3-hexenyl benzoate (4.9 and 9.4%), benzyl alcohol (7.7 and 8.4%), linalool (10.6 and 6.3%), and methyl anthranilate (5.0 and 4.7%). The major volatile constituents of Egyptian J. sambac absolute are almost qualitatively similar but quantitatively different from those grown in other geographical regions. The proportion of some major volatile constituents at this investigation are also different from those reported in a previous investigation for Egyptian J. sambac. The study also revealed that, headspace-solid phase microextraction (HS-SPME), equipped with a polydimethylsiloxane (PDMS) fiber, can give an indication about the composition of some of the major volatile constituents of J. sambac, e.g., indole, methyl anthranilate and E-E-alpha-farnesene, directly from the concrete HS.