Hydroquinone (H₂Q) and chromium (Cr) are commonly used in semiconductor manufacturing processes, tanning, paint, etc., and they are the major environmental pollutants in industrial wastewaters. Hydroquinone was also found as the intermediate product in phenol-containing wastewaters. Chromium(VI) is a toxic and carcinogenic substance with high mobility, and it will cause mutagenic effects to organisms. Therefore, Cr(VI) reduction by organic compounds is one of the major pathways to alleviate the toxicity and mobility of Cr(VI) in the wastewaters. However, the oxidative products of organic compounds receive less scientific attentions. In this study, H₂Q was used as a representative of the organic compound to determine the redox interactions with Cr(VI) in the dark and the concomitant oxidative products. Results showed that while 3.5 mg L^-1 Cr(VI) reacted with 20 mg L^-1 H₂Q, 1,4-benzoquinone (BQ) was the only organic product. In the high concentration system with 400-1600 mg L^-1 of H₂Q and 105 mg L^-1 of Cr(VI), spectroscopic analyses indicated that an oxidative polymerization of organic molecules occurred accompanied with the productions of Cr(III)-enriched organic polymers. The BQ was probably the primary intermediate of H₂Q that induced the subsequent oxidative polymerization in the presence of Cr(VI). The linear combination fitting (LCF) for Cr K-edge X-ray absorption near edge structure (XANES) spectra demonstrated that the organic polymers consisted of 78.0-90.4% Cr(III)-humic-like polymers, suggesting that Cr(III) may act as a linkage of the organic molecules during the polymerization processes of H₂Q.