The high volumetric energy density of rechargeable Mg batteries (RMBs) gives them a competitive advantage over current Li ion batteries, which originates from the high volumetric capacity (∼3833 mA h cm–3) of bivalent Mg metal anodes (MMAs). On the other hand, despite their importance, there are few reports on research strategies to improve the electrochemical performance of MMAs. This paper reports that catalytic carbon nanosubstrates rather than metal-based substrates, such as Mo, Cu, and stainless steel, are essential in MMAs to improve the electrochemical performance of RMBs. In particular, three-dimensional macroporous graphitic carbon nanosubstrates (GC-NSs) with high electrical conductivities can accommodate Mg metal with significantly higher rate capabilities and Coulombic efficiencies than metal substrates, resulting in a more stable and longer-term cycling performance over 1000 cycles. In addition, while metal-based substrates suffered from undesirable Mg peeling-off, homogeneous Mg metal deposition is well-guided in GC-NSs owing to the better affinity of the Mg2+ ion. These results are supported by density functional theory calculations and ex-situ characterization.