PVA/ZnO nanofibrous composite polymer was synthesized as a novel sorbent via electrospinning method at ambient conditions. Physicochemical characteristics of the samples were analyzed using XRD, SEM, EDS, TGA/DSC, and BET techniques. Efficiency of the composite samples for arsenic removal [i.e., As (III) and As (V) anions] was studied under different conditions using RSM optimization approach. Experimental results of adsorption tests indicated that the synthesized PVA/ZnO polymer with the maximum removal of 97% is a highly efficient sorbent for arsenic comparable with other sorbents studied for arsenic removal. The effect of some cations on arsenic removal was also studied in this research. Results showed that the tested ions do not cause a significant reduction in the removal rate. PVA/ZnO composite polymer, which is highly biocompatible, can be considered as a new adsorbent for removal of arsenic from contaminated water.