Reducing the size of titania (TiO2) to the nanoscale promotes the photoactive anatase phase for use in a range of applications from industrial catalysis to environment remediation. The nanoscale dimensions of these systems affect the magnitude of the electronic energy gap by quantum confinement. Upon interaction with aqueous environments or water vapour, the surfaces of these systems will also be hydroxylated to some degree. In turn, this affects the electronic energy levels due to the cumulative electrostatic effect of the dipolar hydroxyl (-OH) ligands (i.e. the ligand dipole effect). Using accurate density functional calculations, we investigate the combined effects of quantum confinement and the hydration-induced ligand dipole effect on a set of realistic titania nanosystems over a wide range of hydroxylation. Our detailed investigation reveals that, contrary to previous models, the ligand dipole effect does not-linearly depend on the ligand coverage due to the formation of inter-ligand OH⋯OH hydrogen bonds. To account for the resulting effects, we propose a refined model, which describes the ligand dipole effect more accurately in our systems. We show that both hydroxylation (by the ligand dipole effect) and size (by quantum confinement) have significant but distinct impacts on the electronic energy levels in nanotitania. As an example, we discuss how variations in these effects can be used to tune the highest unoccupied energy level in nanotitania for enhancing the efficiency of the hydrogen evolution reaction. Overall, we show that any specific energy shift can be achieved by a range of different combinations of nanosystem size and degree of hydroxylation, thus providing options for energy-level tuning while also allowing consideration of practical constraints (e.g. synthetic limitations, operating conditions) for photochemical applications.