Mg²⁺-derived mesoporous ultra-high silica twelve-membered-ring zeolites with multiple topologies (MOR, BEA and MTW) were straightforwardly synthesized by a one-pot route, where the crucial step was the co-hydrolysis/condensation of silica source and magnesium salt under moderate acidic conditions. SiO₂/Al₂O₃ ratios can be adjusted from ∼30 to as high as 410, thus generating superior basicity that was further improved by the incorporation of Mg species. A mesoporous structure was self-formed without the assistance of any template or special strategy. Catalysis tests showed high activity of these zeolites in a typical base reaction, Knoevenagel condensation, even for the bulky substrates due to the enhanced mass transfer arising from the mesopores. This methodology provides a promising approach towards target synthesis of valuable Mg²⁺-derived mesoporous ultra-high silica zeolites with tunable acid/base properties, which can even act as an efficient mesoporous zeolitic solid base.