Abstract: Head-space gas chromatography in hyphenation with mass spectrometry was used in the determination of 9 volatile halogen substituted hydrocarbons (VXH′s). Sample of leather (1.000 g, in slices with dimensions of 0.5 cm ×0.5 cm×1 mm) was equilibrated in a head-space bottle at 110 ℃ for 45 min, and 1 mL of sample was introduced into the instrument for analysis. GS-Gaspro capillary column was used in the separation with programed temperature elevation from 80 ℃ to 250 ℃. In MS determinations, EI (230 ℃), whole scanning mode (35-350 amu) and external standard method were adopted. Linear relationships between values of response signals and masses of the 9 VXH′s were obtained in definite ranges with values of correlation coefficients of their linear regression equations larger than 0.995. Values of lower limits of determination (10S/N) were found in the range of 1-2 mg·kg-1. Tests for recovery were made by standard addition method on the base of leather samples, values of recovery found were ranged from 82.5% to 106%, with values of RSD′s (n=6) ranged from 2.4% to 6.2%.