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The paper presents the results of study of metalliferous (ferromanganese and manganese) rocks at the Nadeiyakha ore occurrence (Pai-Khoi) discovered in 2010. The metalliferous deposit represents a stratiform body lying conformably in the Upper Devonian carbonaceous siliceous and clayey–carbonate–siliceous shales. The ore bed occurs 180 m below the regional Famennian manganiferous rock association in Pai-Khoi. Discovery of the Nadeiyakha ore occurrence suggests the existence of an additional age interval of Mn accumulation within the Devonian sequence of this region. The studied metalliferous rocks display structures and textures typical of the metasedimentary rocks. In terms of composition, they are divided into two varieties: (i) ferromanganese (quartz–carbonate) rocks composed of quartz, dolomite, kutnahorite, rhodochrosite, siderite, and calcite; (ii) manganiferous (quartz–rhodochrosite–silicate) rocks composed of quartz, rhodochrosite, tephroite, sonolite, and pyroxmangite. The Nadeiyakha ore occurrence is marked by the abundance of dolomite in the ferromanganese rocks and host shales. In terms of the relationship of indicator elements (Al, Ti, Fe, and Mn), ferromanganese and manganese rocks are comparable with the recent metalliferous and ore-bearing sediments. The carbon isotope composition in carbonates (δ13C from –16.4 to –7.8‰ PDB) corresponds to authigenic carbonates related to the involvement of carbon dioxide produced during the microbial decomposition of organic matter at the stage of dia- and/or catagenesis. Geological and petrographic observations show that the ferruginous and manganiferous sediments were deposited synchronously with the terrigenous–carbonate–siliceous sediments. Fe and Mn could be sourced from hydrothermal solutions or interstitial diagenetic waters. The latter version seems to be more probable. Metals were accumulated in a depression-trap characterized by a periodic stagnation of bottom waters. Such sedimentation setting promoted the formation of paragenetic association of ferruginous and manganiferous sediments with the carbonaceous sediments and fostered reductive conditions during the postsedimentary mineral formation. Calcium carbonates contained in the primary rocks were subjected to dolomitization during the dia- or catagenesis. This process was promoted by the mobilization of Mg released during the transformation of clay minerals owing to the montmorillonite–illite transition. Iron and manganese carbonates were formed during the later replacement of oxides of Mn3+, Mn4+, and Fe3+. Crystallization of manganese silicates also started at early stages of lithogenesis and terminated during the regional metamorphism of metalliferous rocks.