For nearly two and a half decades following World War II, production wastes from the world’s largest manufacturer of technical DDT were discharged into sewers of Los Angeles County. Following treatment, the wastes were released via a submarine outfall system to nearshore coastal waters where a portion accumulated in shallow sediments of the Palos Verdes Shelf (PVS). An investigation of the pore-water geochemistry of DDT-related compounds (DDX) was undertaken in an effort to understand factors controlling the rate of reductive dechlorination (RDC) of the major DDT degradate, 4,4’-DDE. Equilibrium matrix-solid phase microextraction (matrix-SPMEeq) combined with automated thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) was used to determine freely dissolved concentrations of ten DDX analytes in sediment cores collected from three locations on the PVS (stations 3C, 6C, 8C, which are 7 km, 2 km, and 0 km, respectively, downcurrent from the outfall system). Pore-water concentrations (ng/L) of the principal DDX compounds involved in RDC were: 3C-DDE: 1.9-7.7, DDMU: 3.1-46, DDNU: 0.45-17; 6C-DDE: 1.8-54, DDMU: 1.6-50, DDNU: 0.42-22; 8C-DDE: 8.7-67, DDMU: 8.7-114, DDNU: 1.4-22. Variations in the spatial distribution of DDX analytes in pore water reflect several factors including proximity to the outfalls, RDC reaction rates, and natural variability in sedimentation and post-depositional transport processes. A comparison of pore-water data produced using matrix-SPMEeq/TD-GC/MS and whole-core squeezing/solvent extraction/liquid injection-GC/MS indicates that the majority of the DDE in the upper sediment column (≤ about 10 cm) is associated with dissolved/colloidal organic matter. Below that depth, freely-dissolved DDE predominates. The principal organic geochemical phase controlling sorption of DDE in PVS sediments are residual hydrocarbons, the vast majority of which originated from petroleum refinery wastes. Organic carbon-normalized sediment-water distribution coefficients (KOC) were calculated from solid-phase and pore-water measurements of DDX and organic carbon. Log KOC values (L/kg) were relatively invariant across the shelf and with depth in the sediment column. Shelf-wide compound-specific coefficients were: DDE: 7.5 ± 0.11, DDMU: 6.92 ± 0.13, DDNU: 6.37 ± 0.19. The spatial uniformity of KOC means that biological exposure and availability of the DDX compounds can, in principle, be estimated from solid-phase chemical measurements.