Long-term sustainable solar energy conversion relies on identifying economical and versatile semiconductor materials with appropriate band structures for photovoltaic and photocatalytic applications (e.g., band gaps of ∼1.5–2.0 eV). Nickel oxide (NiO) is an inexpensive yet highly promising candidate. Its charge-transfer character may lead to longer carrier lifetimes needed for higher efficiencies, and its conduction band edge is suitable for driving hydrogen evolution via water-splitting. However, NiO’s large band gap (∼4 eV) severely limits its use in practical applications. Our first-principles quantum mechanics calculations show band gaps dramatically decrease to ∼2.0 eV when NiO is alloyed with Li2O. We show that LixNi1−xO alloys (with x=0.125 and 0.25) are p-type semiconductors, contain states with no impurity levels in the gap and maintain NiO’s desirable charge-transfer character. Lastly, we show that the alloys have potential for photoelectrochemical applications, with band edges well-placed for photocatalytic hydrogen production and CO2 reduction, as well as in tandem dye-sensitized solar cells as a photocathode.