The excellent catalytic performance and high stability of MgO-NiO solid solution catalysts in CH4 conversion to syngas generated the recent outburst of interest for the binary MgO-based solid solutions. This review will focus on the relationship between the catalytic performance of the binary MgO-based solid solution and its properties in the CO2 reforming, the partial oxidation and the steam reforming of methane. First, the development of methane conversion to syngas will be summarized. Second, the role of the basicity and of the solid solution in the design of a catalyst that can inhibit carbon deposition and active metal sintering will be examined. Third, the main results regarding the catalytic performance of the MgO-based solid solutions will be presented. Fourth, detailed information regarding the effects of the NiO/MgO composition, surface area, pore distribution, crystal lattice parameter, precursors, and preparation condition on its catalytic behavior will be provided.