Anthracene belongs to the polycyclic aromatic hydrocarbon (PAH) consisting of benzene rings, unusually highly stable through more π-electrons and localized π-bond in entire rings. Aqueous-phase anthracene adsorption using carbon-based materials such as biochar is ineffective. In this paper, carbon dots (CDs) derived from the acid treatment of coconut shell biochar (CDs/MCSB) decorated with chitosan (CS) are successfully synthesized and applied for anthracene removal from aqueous solutions. The h-CDs/MCSB exhibited fast adsorption of anthracene with significant sorption capacity (Qmax = 49.26 mg g-1) with 95 % removal efficiency at 60 min. The study suggested chemisorption dominated monolayer anthracene adsorption onto h-CDs/MCSB, where a significant role was played by ion-exchange. Density Functional Theory (DFT) suggested the anthracene adsorption was dominated by the electrostatic interactions and delocalized electron, induced by higher polarizability of functional groups on the surface of hybrid CDs/MCSB assisted by chitosan (h-CDs/MCSB). In addition, the aromatic structure of CDs/MCSB and high polarizability of functional groups provided the strong interactions between benzene rings of anthracene and hybrid adsorbent-assisted multiple π-bond through delocalized π-bond and polarization-induced H-bond interactions. The presence of carboxylic and sulfonic groups on the CDs/MCSB surface also contributed to the effective adsorption of anthracene was confirmed by the fluorescence spectra. The results showed that the hybrid adsorbent was an effective material for removing PAHs, usually difficult to remove from water owing to the presence of benzene rings in their structures. Further, consistency in the DFT results suggested the outstanding binding capacity with the anthracene molecules with h-CDs/MCSB.