This paper presents the results of a column reactor test, aiming at evaluating the performance of a biological permeable barrier made of low-cost waste materials, for Cr(VI) removal from contaminated groundwater. A 1:1 by volume mixture of green compost and siliceous gravel was tested as reactive medium in the experimental activity. A 10mg/l Cr(VI) contaminated solution was used and the residual Cr(VI) concentration along the column height and in the outlet was determined in the water samples collected daily. Also pH, redox potential and COD were analyzed. At the end of the test, the reactive medium was characterized in terms of Cr(VI) and total chromium. The Cr(VI) removal efficiency was higher than 99% during the entire experimental activity. The influence of the biological activity on Cr(VI) removal efficiency was evaluated by varying the organic carbon and nitrogen dosages in the contaminated solution fed to the system; a removal decrease was observed when the organic carbon was not enough to sustain the microbial metabolism. The Cr(VI) removal was strictly linked to the biological activity of the native biomass of compost. No Cr(III) was detected in the outlet: the Cr(III) produced was entrapped in the solid matrix. Two main processes involved were: adsorption on the organic-based matrix and reduction into Cr(III) mediated by the anaerobic microbial metabolism of the bacteria residing in green compost. Siliceous gravel was used as the structure matrix, since its contribution to the removal was almost negligible. Thanks to the proven efficiency and to the low-cost, the reactive medium used can represent a valid alternative to conventional approaches to chromium remediation.