Embedding cubane M4(OH)4 (M=Ni, Co) clusters within the matrix of metal–organic frameworks (MOFs) is a strategy to develop materials with unprecedented synergistic properties. Herein, a new material type based on the pore‐space partition of the cubic primitive minimal‐surface net (MOF‐14‐type) has been realized. CTGU‐15 made from the Ni4(OH)4 cluster not only has very high BET surface area (3537 m2 g−1), but also exhibits bi‐microporous features with well‐defined micropores at 0.86 nm and 1.51 nm. Furthermore, CTGU‐15 is stable even under high pH (0.1 m KOH), making it well suited for methanol oxidation in basic medium. The optimal hybrid catalyst KB&CTGU‐15 (1:2) made from ketjen black (KB) and CTGU‐15 exhibits an outstanding performance with a high mass specific peak current of 527 mA mg−1 and excellent peak current density (29.8 mA cm−2) at low potential (0.6 V). The isostructural cobalt structure (CTGU‐16) has also been synthesized, further expanding the application potential of this material type. Split pores: A new 3D microporous metal–organic framework containing cubane Ni4(OH)4 clusters can serve as an electrocatalyst for the methanol oxidation reaction (MOR). The optimal hybrid material shows impressive electrocatalytic performance including a high mass specific peak current of 527 mA mg−1 and excellent peak current density (29.8 mA cm−2) at a very low potential (0.6 V).