Fault-controlled dolomitization has been documented in Lower Carboniferous (Viséan) platform carbonates at various localities in the Pennine Basin and North Wales. The largest of these dolomite bodies (approx. 60 km2) occurs on the Derbyshire Platform, on the southern margin of the Pennine Basin. This study tests the hypothesis that dolomitization occurred at this locality during deposition, platform drowning, and the earliest stages of burial, coincident with the transition from a late syn-rift to post-rift regime. It also assesses the importance of syn-rift volcanism on dolomitization. Planar, fabric-retentive dolomite with single-phase (i.e., low temperature) fluid inclusions occurs along NW–SE and E–W oriented faults, and in platform margin facies and in proximity to the Masson Hill Volcanic Complex. Oxygen isotope data are consistent with dolomitization from seawater, but slightly depleted δ13C values reflect mixing with magmatic fluids. Volcanic activity is likely to have produced a thermal drive for fluid circulation on the platform margin, and post-depositional alteration of basalts by CO2-rich fluids could have led to alteration of olivine and release of magnesium to convecting seawater. Consequently, the large volume of dolostone on the southern margin of the Derbyshire Platform is attributed to the increased geothermal gradient and a localized increase in the Mg/Ca ratio of dolomitizing fluids at this locality, compared to elsewhere in the Pennine Basin. The results suggest that syn-rift carbonate platforms in volcanically active areas of rift basins have a greater potential for dolomitization from seawater than non-volcanic platforms in the same basin.