We report an efficient method for a formal anti-Markovnikov addition of water to styrenes through photocatalytic generation of redox equivalents, using a gold-doped titanium dioxide (Au/TiO2) semiconductor as photocatalyst. Under irradiation with UV-A light, the photocatalytic activity of Au/TiO2 generates in situ under aerobic conditions hydrogen peroxide (H2O2) and under anaerobic conditions dihydrogen (H-2). In the presence of oxygen and a Ru catalyst, the epoxidation of different styrene derivatives is achieved. Subsequently, regioselective reductive Pd-catalyzed epoxide opening in the absence of oxygen gives the corresponding 2-phenylethanol derivatives.