We present the first study of quantifying the diffusion coefficient of interfacial water oil polyelectrolyte surfaces of systems fully dispersed in bulk water under ambient conditions. Such measurements were made possible through the implementation of a recently introduced dynamic nuclear polarization (DNP) technique to selectively amplify the nuclear magnetic resonance (NMR) signal of hydration water that is interacting with specifically located spin-labels on polyelectrolyte surfaces. The merit of this novel capability is demonstrated in this report through the measurement of solvent microvisosity on the surface of two types of oppositely charged polyelectrolytes: when freely dissolved versus when complexed to form a liquid-liquid colloidal phase called complex coacervates. These complex coacervates were formed through electrostatic complexation between the imidazole-based cationic homopolymer poly(N-vinylimidazole) (PVIm) and anionic polypeptide polyaspartate (PAsp) in the pH range of 4.5-6.0, under which conditions the coacervate droplets are highly fluidic yet densely packed with polyelectrolytes. We also investigated the rotational diffusion coefficients of the spin-labels covalently bound to the polyelectrolyte chains for both Mill and PAsp, showing a 5-fold change in the rotational correlation time as well as anisotropy parameter upon coacervation, which represents a surprisingly small decrease given the high polymer concentration inside the dense microdroplets. For both DNP and ESR experiments, the polymers were covalently tagged with stable nitroxide radical spin-labels (similar to 1 wt %) to probe the local solvent and polymer segment dynamics. We found that the surface water diffusion coefficients near uncomplexed PVlm and PAsp at pH 8 differ and are around D similar to 1.3 x 10(-9) m(2)/S. In contrast, inside the complex coacervate phase, the water diffusion coefficient in the immediate vicinity of either polyelectrolyte was D similar to 0.25 x 10(-9) m(2)/s, which is about in order of magnitude smaller than the bulk water self-diffusion coefficient and yet orders of magnitude greater than that of associated, bound, hydration water. This observation suggests the existence of measurable water inside complex coacervates with relatively high diffusion and exchange dynamics, implying that water moves in nanometer-scale pore spaces as opposed to being structurally bound or even absent. We infer from our observation that the PVlm and PAsp chains are undergoing roughly pairwise association, so that largely charge-neutralized species compose the concentrated., yet fluidic, and partially hydrated coacervate cores.