As one of the most significant natural polymer with the highest annual yield, lignin has been applied in the treatment of wastewater to remove heavy metal ions. However, there are still some shortages, such as low reactivity, difficulties in adsorbing oxyanions and low selectivity on specific oxyanions. To improve its adsorption properties, a novel lignin-based adsorbent was prepared in this study, doped with nitrogen by Mannich reaction, using triethylenetetramine (TETA) as N source, and further modified with Ca²⁺. The adsorption of Ca, N-co-doped lignin (Ca@N-Lig) for As (V), Cr (VI) and P (V) was studied. The Ca@N-Lig shows high capacity, excellent selectivity and prominent regeneration ability for As (V) adsorption. The adsorption of Ca@N-Lig for As (V) followed the Langmuir isotherm model and the pseudo-second-order kinetics model, yielding a maximum adsorption capacity of 681.59 mg·g⁻¹ and a fast adsorption equilibrium within 30 min. Ca@N-Lig has an excellent regeneration ability on the adsorption of As (V) with a decrease of about 15.60% after 5 adsorption/desorption cycles. This study offers an efficient way to remove As (V) from polluted water.