A novel and simple strategy was proposed to prepare molecularly imprinted polymer (MIPs) nanocomposites consisting of both conducting polypyrrole (PPy) and a new two-dimensional layered graphene-like black phosphorene quantum dots (BPQDs) onto the surface of conducting poly(3,4-ethylenedioxythiophene) nanorods (PEDOTNRs) via the electrochemical polymerization. The negatively charged BPQDs and template molecules vitamin C (VC) were self-assembled on the surface of the positively charged PEDOTNRs, then the functional monomer pyrrole was also self-assembled with template molecules. A novel molecularly imprinted electrochemical sensor based on PPy-BPQDs-MIPs/PEDOTNRs/GCE was successfully fabricated by the electrochemical polymerization of pyrrole in the presence of VC and BPQDs. The structure and morphology of the prepared MIPs electrode were characterized by transmission electron microscope, scanning electron microscopy, energy dispersive X-ray spectroscopy, and its parameters such as electropolymerization cycles, pH buffer solution, concentrations of template molecules and incubation time were optimized. Under the optimized conditions, the peak currents recorded by differential pulse voltammetry (DPV) demonstrated a linear proportional on VC concentrations ranging from 0.01 to 4 mM with a detection limit of 0.0033 mM. Moreover, the prepared imprinted electrode exhibited a good reproducibility, repeatability stability and selectivity for the electrochemical analysis of VC, which was successfully applied to detect VC in commercial drink soft samples.