This work reveals the As(V) adsorption behaviors onto iron oxide (Fe3O4) nanoparticles modified activated carbon (AC), originally developed from biochar (BC), as a green adsorbent denoted by FAC. Since FAC has abundant surface functional groups and a desired porous structure that is favorable for the removal of As(V) in contaminated water, FAC has greatly enhanced the As(V) adsorption capacity of the original BC. Various methods were employed to characterize the FAC characteristics and adsorption mechanism, including pHpzc determination, BET specific surface area, elemental analysis (EA), and scanning electron microscopy (SEM). Results show that the AC surface was successfully modified by iron oxide nanoparticles, enhancing the porosity and specific surface area of original adsorbent. Batch adsorption tests indicated a well-fitted Langmuir model and pseudo-second-order model for As(V) adsorption. Additionally, the highest adsorption capacity (Qmax = 32.57 mg/g) by FAC was higher than previously reported literature reviews. Until now, no article was conducted to research the effect of carbon surface chemistry and texture on As removal from waters. It is required to obtain a rational view of optimal conditions to remove As from contaminated water.