Shales of very low metamorphic grade from the 2.78 to 2.45 billion-year-old (Ga) Mount Bruce Supergroup, Pilbara Craton, Western Australia, were analyzed for solvent extractable hydrocarbons. Samples were collected from ten drill cores and two mines in a sampling area centered in the Hamersley Basin near Wittenoom and ranging 200 km to the southeast, 100 km to the southwest and 70 km to the northwest. Almost all analyzed kerogenous sedimentary rocks yielded solvent extractable organic matter. Concentrations of total saturated hydrocarbons were commonly in the range of 1 to 20 ppm (μg/g rock) but reached maximum values of 1000 ppm. The abundance of aromatic hydrocarbons was ∼1 to 30 ppm. Analysis of the extracts by gas chromatography-mass spectrometry (GC-MS) and GC-MS metastable reaction monitoring (MRM) revealed the presence of n-alkanes, mid- and end-branched monomethylalkanes, ω-cyclohexylalkanes, acyclic isoprenoids, diamondoids, tri- to pentacyclic terpanes, steranes, aromatic steroids and polyaromatic hydrocarbons. Neither plant biomarkers nor hydrocarbon distributions indicative of Phanerozoic contamination were detected. The host kerogens of the hydrocarbons were depleted in 13C by 2 to 21‰ relative to n-alkanes, a pattern typical of, although more extreme than, other Precambrian samples. Acyclic isoprenoids showed carbon isotopic depletion relative to n-alkanes and concentrations of 2α-methylhopanes were relatively high, features rarely observed in the Phanerozoic but characteristic of many other Precambrian bitumens. Molecular parameters, including sterane and hopane ratios at their apparent thermal maxima, condensate-like alkane profiles, high mono- and triaromatic steroid maturity parameters, high methyladamantane and methyldiamantane indices and high methylphenanthrene maturity ratios, indicate thermal maturities in the wet-gas generation zone. Additionally, extracts from shales associated with iron ore deposits at Tom Price and Newman have unusual polyaromatic hydrocarbon patterns indicative of pyrolytic dealkylation.The saturated hydrocarbons and biomarkers in bitumens from the Fortescue and Hamersley Groups are characterized as 'probably syngenetic with their Archean host rock' based on their typical Precambrian molecular and isotopic composition, extreme maturities that appear consistent with the thermal history of the host sediments, the absence of biomarkers diagnostic of Phanerozoic age, the absence of younger petroleum source rocks in the basin and the wide geographic distribution of the samples. Aromatic hydrocarbons detected in shales associated with iron ore deposits at Mt Tom Price and Mt Whaleback are characterized as 'clearly Archean' based on their hypermature composition and covalent bonding to kerogen.