A novel, metal-free electrode based on heteroatom (S, N, P, O)-doped carbon nanoplates (SNPO-CPL) modifying lead pencil graphite (LPG) has been synthesized by carbonizing a unique heteroatom (S, N, P, O)-containing novel polymer, poly(cyclcotriphosphazene-co-2,5-dioxy-1,4-dithiane) (PCD), for precise screening of dopamine (DA). The designed electrode, SNPO-CPL-800, with optimized percentage of S, N, P, O doping through the sp2-carbon chain, and a large number of surface defects (thus leading to a maximum exposition number of catalytic active sites) led to fast molecular diffusion through the micro-porous structure and facilitated strong binding interaction with the targeted molecules in the interactive signaling transducer at the electrode–electrolyte interface. The designed SNPO-CPL-800 electrode exhibited a sensitive and selective response towards DA monitoring, with a limit of detection (LOD) of 0.01 nM. We also monitored DA levels in commercially available chicken samples using the SNPO-CPL-800 electrode even in the presence of interfering species, thus proving the effectiveness of the designed electrode for the precise monitoring of DA in real samples. This research shows there is a strong potential for opening new windows for ultrasensitive DA monitoring with metal-free electrodes.