AbstractNickel/nanoporous carbon (Ni/NPC) composites are facilely prepared by direct pyrolysis of nonporous heterobimetallic zinc–nickel–terephthalate frameworks (Zn1−xNixMOF, x≈0–1, MOF=metal–organic framework) at 1223 K in situ. Tailoring the Ni/Zn ratio creates densely populated and small Ni nanocrystals (Ni NCs) while maintaining sufficient porosity and surface area in the final product, which exhibits the largest activity factor (9.2 s−1 g−1) and excellent stability toward 4‐nitrophenol reduction.