A new method for the nuclear magnetic resonance (NMR) surface relaxivity calibration in hydrated cement samples is proposed. This method relies on a combined analysis of 28-d hydrated tricalcium silicate samples by scanning electron microscopy (SEM) image analysis and 1H-time-domain (TD)-NMR relaxometry. Pore surface and volume data for interhydrate pores are obtained from high resolution SEM images on surfaces obtained by argon broad ion beam sectioning. These data are combined with T2 relaxation times from 1H-TD-NMR to calculate the systems surface relaxivity according to the fast exchange model of relaxation. This new method is compared to an alternative method that employs sequential drying to calibrate the systems surface relaxivity.