A method is developed for determining the optical properties of an optically rough coating on an opaque substrate from reflectance measurements. A modified Kubelka-Munk two- flux model is used to calculate the reflectance of the coating as a function of the refractive index, absorption coefficient, scattering coefficient, and thickness. The calculated reflectance is then fitted to measurements using a spectral projected gradient algorithm, allowing the optical properties to be obtained. The technique is applied to titanium dioxide coatings on a titanium substrate. Realistic values of refractive index and absorption coefficients are generally obtained. Quantities that are useful for solar water-splitting applications are calculated, including the depth profile of absorption and the proportion of the incident photon flux absorbed in the coating under solar illumination.