Evaluating the catalytic influence of metal sites on derivates obtained from the calcination of metal–organic frameworks (MOFs) is very important for the rational construction of novel MOFs. Based on this catalytic functional guidance, two new Co-MOF and CoNi-MOF crystals were designed and synthesized, and further pyrolyzed to obtain corresponding porous carbon-based catalysts. Interestingly, the derivates exhibited better catalytic performance toward the tandem reaction of dehydrogenation of NH₃BH₃ and subsequent hydrogenation reduction of nitro/olefin compounds than those of the CoNi-ZIF (a star MOF)-derived CoNi@carbon and most metal catalysts. Significantly, the CoNi@C maintained excellent activity, even after 30 cycles, demonstrating its great longevity and durability, which are especially important for the practical application of metal catalysts in industrial catalysis.