© 2016, Springer-Verlag Berlin Heidelberg.Cosmic ray exposure (CRE) dating was performed on the caldera cliffs of Santorini with the aim of detecting cliff segments predating the Minoan eruption (17th century BCE). The methodology involved the determination of in situ-produced cosmogenic 36Cl concentration in basaltic-to-rhyodacitic whole rocks cropping out in the cliffs. After the samples were processed following the chemical protocol of 36Cl preparation for silicate rocks, 36Cl concentrations were measured by accelerator mass spectrometry (AMS). Important challenges during the implementation procedure were related to large amounts of radiogenic 36Cl, complex modeling of inherited 36Cl, and dominance of the thermal and epithermal (low-energy) neutron capture production pathway. Nevertheless, quantitative assessments on the basis of the contribution of the low-energy neutron capture pathway percent to the total production rate validated the calculated CRE dates. Current CRE ages demonstrate that an ancient caldera existed on pre-Minoan Santorini, occupying at least the northern half of the modern-day caldera.