We show enhanced efficiency and stability of a high performance organic solar cell (OPV) when the work-function of the hole collecting indium-tin oxide (ITO) contact, modified with a solution-processed nickel oxide (NiOx) hole-transport layer (HTL), is matched to the ionization potential of the donor material in a bulk-heterojunction solar cell. Addition of the NiOx HTL to the hole collecting contact results in a power conversion efficiency (PCE) of 6.7%, which is a 17.3% net increase in performance over the 5.7% PCE achieved with a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) HTL on ITO. The impact of these NiOx films is evaluated through optical and electronic measurements as well as device modeling. The valence and conduction band energies for the NiOx HTL are characterized in detail through photoelectron spectroscopy studies while spectroscopic ellipsometry is used to characterize the optical properties. Oxygen plasma treatment of the NiOx HTL is shown to provide superior contact properties by increasing the ITO/NiOx contact work-function by 500 meV. Enhancement of device performance is attributed to reduction of the band edge energy offset at the ITO/NiOx interface with the poly(N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothidiazole) (PCDTBT):[6,6]-phenyl-C61 butyric acid methyl ester PCBM and [6,6]-phenyl-C71 butyric acid methyl ester (PC70BM) active layer. A high work-function hole collecting contact is therefore the appropriate choice for high ionization potential donor materials in order to maximize OPV performance.