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We present geochemical characteristics of the Lower Palaeozoic shales deposited in the Baltic Basin and Podlasie Depression. In the study area, this strata are represented by the Upper Cambrian–Lower Ordovician Alum Shale recognized in southern Scandinavia and Polish offshore and a equivalent the Lower Tremadocian Dictyonema Shale from the northern Estonia and the Podlasie Depression in Poland. Geochemical analyses reveal that the Alum Shale and Dictyonema Shale present high contents of organic carbon. These deposits have the best source quality among the Lower Palaeozoic strata, and they are the best source rocks in the Baltic region. The bituminous shales complex has TOC contents up to ca. 22 wt%. The analysed rocks contain low-sulphur, oil-prone Type-II kerogen deposited in anoxic or sub-oxic conditions. The maturity of the Alum and Dictyonema Shales changes gradually, from the east and north-east to the west and south-west, i.e. in the direction of the Tornquist-Teisseyre Zone. Samples, located in the seashore of Estonia and in the Podlasie region, are immature and in the initial phase of “oil window”. The mature shales were found in the central offshore part of the Polish Baltic Basin, and the late mature and overmature are located in the western part of the Baltic Basin. The Alum and Dictyonema Shales are characterized by a high grade of radioactive elements, especially uranium. The enrichment has a syngenetic or early diagenetic origin. The measured content of uranium reached up to 750 ppm and thorium up to 37 ppm. © 2016, Springer-Verlag Berlin Heidelberg.