The direct photocatalytic conversion of methane into methanol with water at room temperature and pressure has attracted particular attention in recent decades. Valuable insight has been obtained into the reaction mechanisms and the key descriptors that control photoactivity and selectivity. This Minireview highlights the different efforts that have been undergone on the design of nanostructured photocatalytic systems to enhance the selectivity to methanol. The effect of structural and electronic aspects, such as surface area, morphologies, crystal facets, redox properties, metal doping, and heterojunctions, on photocatalytic performance, are discussed. The roles of free hydroxyl radicals and/or hydroxy groups for methane activation on the photocatalyst surface are also presented. This Minireview aims to provide an insight into the optimal properties and configurations of the nanostructured photocatalytic materials for tuning their reactivity on the selective oxidation of CH4 to methanol with water. The remaining challenges and promising directions for bringing this technology a step closer to real‐world application are also highlighted.