This paper highlights the use of synkinematic white mica, biotite and phlogopite for the dating of deformation in ductile shear zones within crystalline rocks under low-grade metamorphic conditions. The Mont Blanc shear zones range from 1 mm to 50 m in width and have localized intense fluid flow, resulting in substantial differences in mineralogy and whole-rock geochemistry. On the basis of their synkinematic alteration assemblages and geographic distribution within the Mont Blanc Massif, three main metamorphic zones are distinguished within the network of shear zones. These are: (i) epidote±white mica-bearing assemblages; (ii) chlorite–phlogopite-bearing assemblages; and (iii) white mica±biotite±calcite±actinolite±epidote- bearing assemblages. 40Ar/39Ar age spectra of biotite and phlogopite are complex, and reflect significant variations in chemical composition. In biotite, this is partly due to inheritance from precursor Variscan magmatic biotite. In contrast, new white mica grew at the expense of feldspar during Alpine deformation and its Ar spectra do not show any excess 40Ar. On the SE side of Mont Blanc, ages of shear zone phengites have a narrow range of 15.8–16.0±0.2 Ma, which is in the same age range as 40Ar/39Ar ages of minerals from kinematically related veins. The top-to-SE sense of shear is consistent with initiation of a Mont Blanc flower-structure within a dextral transpressional system by 16 Ma. On the NW side, mini-plateaux ages of 14.5±0.3 and 23.4±0.4 Ma are preserved in the same sample, suggesting the possibility of two phases of deformation. This is also supported by partly preserved ages of 18–36.6 Ma in biotites and phlogopites. Ages between 36 and 18 Ma might reflect ongoing top-to-NW thrusting, following Penninic Front activation, in a context of nappe stacking and crustal thickening. NW-directed thrusting on the NW side of Mont Blanc continued after 18 Ma, synchronous with SE-directed thrusting on the SE side of the massif. These divergent movements produced the overall pop-up geometry of the Mont Blanc Massif, which may correspond to a positive flower structure developed within a zone of regional dextral transpression extending SW from the Rhone valley into the Mont Blanc area.