Within the continent-ocean transition several nonvolcanic rifted margins exhibit a zone of partially serpentinized peridotites which continue under the thinned and faulted continental crust and are thought to represent subcontinental lithosphere serpentinized by contact with water. As water in sufficient volumes can only come from the surface, we suggest that a major condition for the onset of serpentinization is the embrittlement of the entire crust during progressive extension and hence the development of active crustal penetrating faults acting as fluid conduits. We investigate this possibility by modeling the rheological evolution of the lithosphere during extension and hence determining at what stretching factors the lower crust enters the brittle regime for a variety of different strain rates and lower crustal rheologies. Using an initial thermal structure appropriate for nonvolcanic margins, we find that the entire crust becomes brittle at stretching factors of between ~3 and 5, depending on the strain rate. This compares well with the thickness of the crust observed just landward of the onset of partially serpentinized peridotites west of Iberia. The predicted thickness of the serpentinized peridotites (depth of the thermal limit of serpentinite stability beneath the crust-mantle boundary) also compares reasonably well with their observed thickness. As serpentinites are characterized by low friction coefficients, we suggest that the onset of mantle serpentinization controls the development of decollements at the crust-mantle boundary such as the S and H reflectors west of Iberia (leading to crustal separation). The development of thick serpentinites probably contributes to the weakening of the upper lithosphere and hence the localization of final breakup.