Over the last century, the industrialization of agriculture and the consumption of fossil fuels have resulted in a significant imbalance and redistribution in nitrogen-containing resources. This has sparked an interest in developing more sustainable and resilient approaches for producing nitrogen containing commodities such as fertilizers and fuels. One largely neglected but emerging approach is photocatalytic nitrogen fixation. There is significant evidence that this process occurs spontaneously in terrestrial settings, and it has been demonstrated in numerous engineered systems. Yet many questions still remain unanswered regarding the rates, mechanisms, and impacts of photocatalytically producing fixed nitrogen "out of thin air". This work reviews the fascinating history of the reaction and examines current progress toward understanding and improving photofixation of nitrogen. This is supplemented by a quantitative review of the thermodynamic considerations and limitations for various reaction mechanisms. Finally, future prospects and preliminary performance targets for photocatalytic nitrogen fixation are discussed.