There is a challenge to boost the electromagnetic wave absorption performance of magnetic carbon-based materials by rationally adjusting the structure of MOF. In this paper, nanoclip-shaped polypyrrole (PPy) was wrapped on the surface of the Co/C nanoparticle derived from Co-MOF via in-situ polymerization of pyrrole with the help of cetylammonium bromide. The electromagnetic parameters of prepared Co/C@PPy can be easily tuned by adjusting the feed ratio of PPy to Co/C. The optimum value of reflection loss (RL) for Co/C@PPy is −45.49 dB at 2.4 mm and 15.12 GHz when the feed ratio of pyrrole to Co/C is 200 μL to 80 mg, and the effective absorption bandwidth (EAB, RL ≤ −10 dB) reaches 5.97 GHz (11.76–17.73 GHz) at the matching thickness of 2.5 mm. This study paves the way for further design and preparation of the nanocomposites based on MOF-derived nanostructures with excellent EMW absorption performance.