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A series of novel C33–C35hexacyclic benzohopanes (C33b-C35b) were identified in 39 samples of coal extracts and 39 crude oils of different ages from all over the world. C33b and C34b homologues were isolated, and their structures were determined by nuclear magnetic resonance. The structure of C35b benzohopane was proposed based on the mass spectrum and its similarity with the mass spectra of structurally defined C33b and C34b homologues. The structures of the C33b-C35b hexacyclic benzohopanes are closely related to isohopanes; both groups are typical for terrestrial organic matter and can be useful in the correlation analysis. A possible pathway of formation of these novel benzohopanes and their hopanoid precursors with an additional branch in the aliphatic side chain is proposed. C33b–C35b hexacyclic benzohopanes are stable up to the maturity level corresponding to random vitrinite reflectance (Rr) of ∼0.80%, which was demonstrated by analyzing the samples of different maturity and by the maturation simulation experiments: hydrous pyrolysis of two bituminous coals (Rr = 0.55 and 0.59%) and pyrolysis of an extracted bituminous coal (Rr = 0.56%) and its asphaltenes. This represents a confirmation that the formation of these novel benzohopanes is related to specific depositional conditions and microbial activity during diagenesis. Mature samples (Rr ≥ 0.8%) and hydrous pyrolysate of the bituminous coals (Rr < 0.60%) obtained at 330 °C show a distinct distribution of benzohopanes in comparison to immature and moderately mature samples, which is characterized by a low abundance of the “b” series benzohopanes and the presence of regular and numerous other benzohopane isomers. The latter most likely represent isomers of regular and novel benzohopanes with different substitution patterns on the aromatic ring. This isomerization of alkyl groups attached to the aromatic ring, leading to the formation of thermodynamically more stable isomers, is a well-known maturation scenario so far reported in the series of alkylated naphthalenes, phenanthrenes, and dibenzothiophenes. Therefore, in the same way, a distribution of benzohopanes can indicate thermal maturity. In addition to the novel benzohopanes, three series (2α, 2β, and 3β) of their methylated derivatives were identified in numerous samples. Finally, a novel C35heptacyclic benzohopane with an additional cyclopentane ring was also observed in the studied samples, and its structure was tentatively identified based on the mass spectrum. Opposite to the hexacyclic C33b–C35b benzohopanes, the formation of the C35heptacyclic benzohopane does not require a specific hopanoid precursor with two branches in the side chain. Therefore, this compound seems to have less geochemical significance than the new hexacyclic benzohopanes.