Abstract: In a headspace-sampling apparatus and method, use is made of a sampling body which defines a sample chamber, first passage means extending from said chamber, means for connecting said passage means to the entry end of a chromatography column held in operative position in a gas chromatograph, second passage means extending to said chamber, and means for connecting a source of gas to said second passage means. When the first-named connection means is connected to the column, a gas flow can be established within the body from the second named connection means through the said chamber to the entry end of the column, whereby a headspace sample of said substance is swept directly from said chamber on to an entry end region of said column, the headspace sample being cumulatively trapped at said region.