The metallization of graphite substrates is currently confronted by negative issues including insufficient adhesion and inherent instability. In an effort to surmount these challenges, a layer of conductive polypyrrole (PPy) film on a graphite surface is formed through simple polymerization, followed by an electroplating copper layer. The graphite enveloped by the PPy film, subjected to cyclic voltammetry (CV) and linear sweep voltammetry (LSV) analyses, demonstrates enhanced electrochemical activity and thus renders the more efficient electrodeposition of copper. Further investigation was conducted through orthogonal experiments to explore the optimal formulation of electroplating solutions containing popular additives including 3, 3′-dithiobis-1-propanesulfonic acid disodium salt (SPS), Janus Green B (JGB), and polyethylene glycol 8000 (PEG8000)., According to the optimal additive formulation, a dense copper layer with superior adhesion was electroplated on the graphite substrate employing PPy as an intermediate layer.