The changes of Np oxidation state in nitric acid and the effect of nitrous acid on the oxidation state were analyzed by spectrophotometry, solvent extraction, and electrochemical methods. An enhancement of Np extraction to 30 vol.% TBP was carried out through adjustment of Np oxidation state by using a glassy carbon fiber column electrode system. The information of electrolytic behavior of nitric acid was important because the nitrous acid affecting the Np redox reaction was generated during the electrolytic adjustment of the Np oxidation state. The Np solution used in this work consisted of Np（V) and Np（Ⅵ）without （IV）. The composition of Np（V) in the range of 0.5M -5.5 M nitric acid was 32% ~ 19%. The electrolytic oxidation of Np（V) to Np（Ⅵ）in the solution enhanced Np extraction efficiency about five times higher than the case without the electrolytic oxidation. It was confirmed that the nitrous acid of less than about 10-5 M acted as a catalyst to accelerate the chemical oxidation reaction of Np（V) to Np（Ⅵ）.