In this study, one well-known CHM residue (Atropa belladonna L., ABL) was used to prepare biochar capable of adsorbing rhodamine B (RhB) with an ultrahigh surface area for the first time. Three micropore-rich ABL biochars including ABL@ZnCl2 (1866 m2/g), ABL@H3PO4 (1488 m2/g), and ABL@KOH (590 m2/g) were obtained using the one-step carbonization method with activation agents (ZnCl2, H3PO4, and KOH) via chemical activation and carbonization at 500 °C, and their adsorption performance for RhB was systematically studied with adsorption kinetics, isotherms, and thermodynamics. Through pore diffusion, π-π interaction, and hydrogen bonding, ABL biochar had excellent adsorption performance for RhB. Moreover, when C 0 was 200 mg/L, biochar dosage was 1 g/L, and the contact time was 120 min; the maximum RhB adsorption capacity and removal efficiency on ABL@ZnCl2 and ABL@H3PO4 were 190.63 mg/g, 95% and 184.70 mg/g, 92%, respectively, indicating that it was feasible to prepare biochar from the ABL residue for RhB adsorption. The theoretical maximum adsorption capacities of ABL@ZnCl2 and ABL@H3PO4 for RhB were 263.19 mg/g and 309.11 mg/g at 25 °C, respectively. Furthermore, the prepared biochar showed good economic applicability, with pay back of USD 972/t (ABL@ZnCl2) and USD 987/t (ABL@H3PO4), respectively. More importantly, even after five cycles, ABL@H3PO4 biochar still showed great RhB removal efficiency, suggesting that it had a good application prospect and provided a new method for the resource utilization of traditional CHM residues. Additionally, pore diffusion, π-π interactions, and hydrogen bonding all play roles in the physical adsorption of RhB on ABL biochar. π-π interactions dominated in the early stage of RhB adsorption on ABL@H3PO4, while pore diffusion played a crucial role in the whole adsorption process on both adsorbents.