In this proof of principle work, a technique is introduced to study hydrated surfaces using hyperpolarized (hp) Kr-83 NMR spectroscopy. The longitudinal (T-1) relaxation of hp-Kr-83 is shown to be extremely sensitive to the presence of adsorbed water on hydrophilic borosilicate and hydrophobic siliconized glass surfaces. The krypton surface relaxation is found to be largely independent of the total gas pressure applied to the studied materials, and the presented technique is therefore fairly robust. However, the relaxational properties of hp-Kr-83 can be "tuned" by adjusting the composition of the optical pumping gas mixture. This effect may be important for practical applications such as hp-Kr-83 MR imaging and can be achieved without sacrificing signal intensity. Complementary information to that of hp-Kr-83 surface relaxation data can be obtained from hp-Xe-129 relaxation measurements that are sensitive to the presence of paramagnetic surface sites. In contrast to the signal decay of hp-Xe-129, the longitudinal relaxation of Kr-83 is largely unaffected by paramagnetic impurities, and in some materials, Kr-83 and Xe-129 show comparable T-1 times that are caused by two completely different relaxation mechanisms. Finally, the relaxation times of Kr-83 in contact with bovine lung surfactant coated glass pores that are similar in size to mammalian alveoli are presented. The results suggest that in vivo MR studies may be feasible and could provide valuable information about changes in pulmonary surface chemistry.