In order to address the question of the processes involved during shear zone nucleation, we present a petro-structural analysis of millimetre-scale shear zones within the Roffna rhyolite (Suretta nappe, Eastern central Alps). Field and microscopic evidences show that ductile deformation is localized along discrete fractures that represent the initial stage of shear zone nucleation. During incipient brittle deformation, a syn-kinematic metamorphic assemblage of white mica + biotite + epidote + quartz precipitated at ca. 8.5 ± 1 kbar and 480 ± 50 °C that represent the metamorphic peak conditions of the nappe stacking in the continental accretionary wedge during Tertiary Alpine subduction. The brittle to ductile transition is characterized by the formation of two types of small quartz grains. The Qtz-IIa type is produced by sub-grain rotation. The Qtz-IIb type has a distinct CPO such that the orientation of c-axis is perpendicular to the shear fracture and basal and rhombhoedric slip systems are activated. These Qtz-IIb grains can either be formed by recrystallization of Qtz-IIa or by precipitation from a fluid phase. The shear zone widening stage is characterized by a switch to diffusion creep and grain boundary sliding deformation mechanisms. During the progressive evolution from brittle nucleation to ductile widening of the shear zone, fluid–rock interactions play a critical role, through chemical mass-transfer, metasomatic reactions and switch in deformation mechanisms.