We study the molecular-scale properties of colloidal water-oil emulsions consisting of 120-290 nm oil droplets embedded in water. This type of emulsion can be prepared with low concentrations of surfactants and is usually kinetically stable. Even though colloidal water-oil emulsions are used ubiquitously, their molecular properties are still poorly understood. Here we study the orientational dynamics of water molecules in these emulsions using polarization resolved pump-probe infrared spectroscopy, for varying surfactant concentrations, droplet sizes, and temperatures. We find that the majority of the water molecules reorients with the same time constant as in bulk water, while a small fraction of the water molecules reorients on a much longer time scale. These slowly reorienting water molecules are interacting with the surface of the oil droplets. The fraction of slowly orienting water molecules is proportional to the oil volume fraction, and shows a negligible dependence on the average droplet size. This finding indicates that the total surface area of the oil droplets is quite independent of the average droplet size, which indicates that the larger oil droplets are quite corrugated, showing large protrusions into the water phase.