In order to obtain more information and to understand the nature of relation between organic and mineral matter in oil shales, the compositions of soluble bitumen fractions obtained by extraction from Bulgarian oil shales before and after demineralization with 10% HCl, concentrated HE and a HF/HCl mixture were investigated. The four extracts were quantitatively examined by IR and H-1 NMR spectroscopy. The investigation of isolated acidic material of the bitumen fractions showed that the fatty acids are present in bitumen fractions as free acids, esters and salts. The amount of free acids in bitumen is very small. The dominant part of bitumen acids is associated with mineral components of the oil shales as well as part of them is included in the mineral matrix, and can be separated only after deep demineralization. The kerogen of the oil shales, obtained after separation of the bitumen fractions and mineral components, was subjected to saponification in order to determine the amount of acids, bound as esters to the kerogen matrix. The major components found were n-carboxylic, alpha,omega,-di-carboxylic, and aromatic acids. The connection of kerogen with mineral components is accomplished by the participation of carboxylic and complicated ester bonds. Experimental data for the composition of bitumen acids give evidence that algae and terrestrial materials are initial sources in the formation of soluble organic matter of Bulgarian oil shale. (C) 2008 Elsevier B.V. All rights reserved.