Surface states of mesoporous NiO semiconductor films have particular properties differing from the bulk and are able to dramatically influence the interfacial electron transfer and adsorption of chemical species. To achieve a better performance of NiO-based p-type dye-sensitized solar cells (p-DSCs), the function of the surface states has to be understood. In this paper, we applied a modified atomic layer deposition procedure that is able to passivate 72% of the surface states on NiO by depositing a monolayer of Al2O3. This provides us with representative control samples to study the functions of the surface states on NiO films. A main conclusion is that surface states, rather than the bulk, are mainly responsible for the conductivity in mesoporous NiO films. Furthermore, surface states significantly affect dye regeneration (with I-/I3- as redox couple) and hole transport in NiO-based p-DSCs. A new dye regeneration mechanism is proposed in which electrons are transferred from reduced dye molecules to intra-bandgap states, and then to I3- species. The intra-bandgap states here act as catalysts to assist I3- reduction. A more complete mechanism is suggested to understand the particular hole transport behavior in p-DSCs, in which the hole transport time is independent of light intensity. This is ascribed to the percolation hole hopping on the surface states. When the concentration of surface states was significantly reduced, the light-independent charge transport behavior in pristine NiO-based p-DSCs transformed into having an exponential dependence on light intensity, similar to that observed in TiO2-based n-type DSCs. These conclusions on the function of surface states provide new insight into the electronic properties of mesoporous NiO films.