Herein, we report an efficient, simple, coherent, and green benign synthesis of the C–P coupling reaction based on the Fe3O4@glutamate MOF functionalized with Co nanoparticle anchored dicyandiamide. The structure of the as‐prepared catalyst was characterized by a series of measurement techniques, including FT‐IR, XRD, BET, TEM, FE‐SEM, EDX, EDX‐mapping, VSM, TGA, and ICP‐OES. The aforementioned nanocatalyst with a unique structure exhibited excellent catalytic performance on various substrates towards the synthesis of C–P cross‐coupled products in good to high yields under mild conditions. This unique heterogeneous catalytic system kept relatively high catalytic activity after five recycle runs under the same reaction conditions.