In situ arsenic removal from groundwater by an aquifer iron coating method has great potential to be a cost effective and simple groundwater remediation technology, especially in rural and remote areas where groundwater is used as the main water source for drinking. The in situ arsenic removal technology was first optimized by simulating arsenic removal in various quartz sand columns under anoxic conditions. The effectiveness was then evaluated in an actual high-arsenic groundwater environment. The arsenic removal mechanism by the coated iron oxide/hydroxide was investigated under different conditions using scanning electron microscopy (SEM)/X-ray absorption spectroscopy, electron probe microanalysis, and Fourier transformation infrared spectroscopy.Aquifer iron coating method was developed via a 4-step alternating injection of oxidant, iron salt and oxygen-free water. A continuous injection of 5.0mmol/L FeSO4 and 2.5mmol/L NaClO for 96h can form a uniform goethite coating on the surface of quartz sand without causing clogging. At a flow rate of 7.2mL/min of the injection reagents, arsenic (as Na2HAsO4) and tracer fluorescein sodium to pass through the iron-coated quartz sand column were approximately at 126 and 7 column pore volumes, respectively. The retardation factor of arsenic was 23.0, and the adsorption capacity was 0.11mol As per mol Fe. In situ arsenic removal from groundwater in an aquifer was achieved by simultaneous injections of As(V) and Fe(II) reagents. Arsenic fixation resulted from a process of adsorption/co-precipitation with fine goethite particles by way of bidentate binuclear complexes. Therefore, the study results indicate that the high arsenic removal efficiency of the in situ aquifer iron coating technology likely resulted from the expanded specific surface area of the small goethite particles, which enhanced arsenic sorption capability and/or from co-precipitation of arsenic on the surface of goethite particles.