The direct Cr (VI) reduction process by oxalic acid was conducted and the results showed that the Cr (VI) was efficiently reduced by oxalic acid at high reaction temperature and high dosage of oxalic acid. The reduced product, Cr (III), was easily generated stable complex compounds (Cr(HC2O4)3) with oxalate, which displayed a negative effect on the reduction process. The high reaction temperature and high acidic medium could destroy the stable structure of a complex compound to release oxalate, and facilitate the reduction of Cr (VI). Generally, the present study provided a versatile strategy for Cr (VI) reduction, exhibiting a bright application future for real wastewater treatment.