AbstractNanoscale zerovalent iron (nZVI) was synthesized and employed for treating chromium(VI) containing aqueous solution through adsorption using a series of microcosm experiments. The experiments were then performed to study the effects of a light nonaqueous phase liquid, toluene, on Cr(VI) removal by nZVI. Results showed that a maximum removal efficiency of almost 90% was achieved within 300 min of the treatment process, while it was suppressed by approximately 25% in toluene’s copresence. The efficiency was found to be higher (>80%) at pH 3–7 and reduced to 30.3% at pH 9. No significant change in the removal was observed due to a change in pH under toluene’s copresence (57%–65% removal for all pH ranges). The removal efficiency also reduced from 62.7% to 37.1% and 82.1% to 28.3% with an increase in Cr(VI) concentration (25–200 mg/L), with and without coexisting toluene, respectively. The surface morphology and structure of nZVI pre- and posttreatment with Cr(VI) and toluene were analyzed through scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The results confirmed the presence of Cr(VI) and toluene on the nZVI surface. The adsorption of Cr(VI) by nZVI was best described by pseudo-second-order kinetics (R2 = 0.97 in both cases) and the Langmuir isotherm equilibrium model (R2 = 0.95, 0.81). The maximum adsorption capacity (Qmax) for Cr(VI) without and with toluene was 64.52 and 58.47 mg/g of nZVI particles, respectively. Findings from this study provide crucial information about cocontamination and its noticeable effects on remediation of the contaminants of concern.