The Jifarah Arch of NW Libya is a structurally prominent feature at the eastern end of the regional Talemzane Arch, separating the Ghadamis hydrocarbon province to the south from the offshore Pelagian province to the north. The Arch has experienced a complex structural history with repeated episodes of uplift, exhumation and burial. This paper provides a provisional assessment of its hydrocarbon habitat based on detailed geochemical analyses of potential Triassic, Silurian and Ordovician source rocks encountered by wells drilled in the area. Twenty-seven core and cuttings samples of marine shales were collected from eight widely- dispersed wells and analyzed using standard Rock-Eval pyrolysis techniques. Kerogen types II-III were identified in the majority of Triassic samples analysed, indicating a low hydrocarbon generation potential, but oil-prone Type II kerogen was found in the basal Silurian Tanezzuft Formation and Ordovician Memouniat Formation. The presence of steranes and acyclic isoprenoids suggested variable inputs of algal, bacterial and terrestrial organic matter, while biomarkers including C-30-gammacerane and -carotene and selected biomarker ratios (Pr/Ph ratio and homohopane index) were used to assess their depositional environment. Results indicate that extended zones with periodic (if not continuous) oxygen-deficient conditions existed throughout the basin during Late Ordovician and Early Silurian time, favouring the preservation of organic matter. The thermal maturity of the samples was assessed by Rock-Eval pyrolysis, zooclast reflectance, molecular ratios including C(32-)22S/(22S+22R)-homohopanes, Ts/(Ts+Tm), C-29-steranes and parameters based on the relative abundance of methylphenanthrene, methyldibenzothiophene and methylnaphthalene isomers. The results indicate significant variability in thermal maturity, with Ordovician and Silurian source rocks ranging from 0.6% to 0.7% VRo equivalent increasing to 1.0% locally. These values represent palaeo-maturities achieved at different times in the past and are considered too low to have generated significant volumes of hydrocarbons directly. However the downdip equivalents of these source rocks in the adjacent Ghadamis Basin contributed to prolific petroleum systems. The absence of large petroleum accumulations on the Jifarah Arch contrasts with the western part of the geologically similar Talemzane Arch, which harbours several giant and supergiant oil and gas fields. This difference is attributed both to the complex structural history of the Jifarah Arch, which permitted post-charge leakage of palaeo-accumulations, and stratigraphic migration barriers which restricted migration between Tanezzuft source rocks and Ordovician and Triassic reservoirs.