Fe-oxide deposits of the Lahn-Dill-type in the eastern Rhenish Massif comprise haematite and quartz with minor siderite, magnetite, and calcite. The deposits are located in the hanging wall of thick volcaniclastic rock sequences and mark the Middle to Late Devonian boundary. Varying ore types with accompanying footwall rocks were sampled from two formerly important ore deposits, the Fortuna mine (Lahn syncline) and the Briloner Eisenberg mine (East Sauerland anticline), in order to elucidate the interplay of processes leading to ore formation. Deposit geology, petrography, and whole-rock geochemistry suggest that the ores formed by iron mobilisation from deeply altered footwall volcaniclastic rocks, subsequent venting of a modified H2O-CO2-Fe-rich and H2S-poor fluid, and precipitation on the seafloor (sedimentary-type), or locally by metasomatic replacement of wall rocks (replacement-type). Petrographic analysis to the sub-micron scale revealed that the sedimentary-type ores most likely formed from a Fe-Si-rich gel and accompanying maturation. Early gel textures include the presence of spherules, aggregates, tubes, and filamentous stalks consisting of nanocrystalline haematite dispersed in a matrix of microcrystalline quartz. Local diagenetic Fe3+ reduction within the gel is indicated by siderite replacement of haematite. Replacement-type ores formed due to a two-step process including coprecipitation of (precursor) haematite and carbonates and subsequent metasomatic replacement by haematite. These ore-forming processes took place during a time when several restricted shallow marine basins in the north-eastern Rheic Ocean were influenced by extensive volcanism and associated hydrothermal fluid flux. Examples of similar volcanic-associated Fe-oxide occurrences of Silurian to Carboniferous age can be categorised as being of Lahn-Dill-type ores as well.