Reference-quality gas chromatographic/matrix isolation/Fourier transform infrared spectra have been recorded for the following fifteen compounds, which collectively are referred to as the “laterally” chlorinated dibenzo- p-dioxins and dibenzofurans: 2,3,7,8-tetrachlorodibenzo- p-dioxin (2,3,7,8-TCDD); 1,2,3,7,8-pentachlorodibenzo- p-dioxin (1,2,3,7,8-PeCDD);l,2,3,4,7,8-hexachlorodibenzo- p-dioxin(1,2,3,4,7,8-HxCDD)>; 1,2,3,6,7,8,-hexachlorodibenzo- p-dioxin(1,2,3,6,7,8-HxCDD); 1,2,3,7,8,9-hexachlorodibenzo- p-dioxin (1,2,3,7,8,9-HxCDD); 1,2,3,4,6,7,8-heptachlorodibenzo- p-dioxin (1,2,3,4,6,7,8-HpCDD); 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF); 1,2,3,7,8-pentachlorodibenzofuran (1,2,3,7,8-PeCDF); 2,3,4,7,8-pentachlorodibenzofuran (2,3,4,7,8-PeCDF); 1,2,3,4,7,8-hexachlorodibenzofuran(1,2,3,4,7,8-HxCDF); 1,2,3,6,7,8-hexachlorodibenzofuran (1,2,3,6,7,8-HxCDF); 1,2,3,7,8,9-hexachlorodibenzofuran (1,2,3,7,8,9-HxCDF); 2,3,4,6,7,8-hexachlorodibenzofuran (2,3,4,6,7,8-HxCDF); 1,2,3,4,6,7,8-heptachlorodibenzofnran (1,2,3,4,6,7,8-HpCDF); and 1,2,3,4,7,8,9-heptachlorodibenzofuran (1,2,3,4,7,8,9-HpCDF). These spectra are discussed qualitatively and, for the laterally chlorinated dioxins, are compared to previously recorded gas-phase GC/FT-IR spectra. Estimates of the instrumental detection limits for these compounds, using matrix isolation GC/FT-IR spectroscopy, were found to fall in the mid-to-high picogram and low nanogram ranges.