In order to separate methylene blue from aqueous solution, a novel method based upon liquid-liquid extraction, using a nonionic surfactant-ionic liquid system as extracting phase, was investigated. A comparative study was carried out with the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, known as [C4mim]PF6. By using the nonionic surfactant-ionic liquid system, the extraction efficiency could reach 97.8%, indicating that the addition of nonionic surfactant (Triton X-114) significantly improves the extraction of methylene blue. Under optimal conditions, the dye concentration in the effluent showed an almost 50-fold reduction. However, the extraction extent of methylene blue was found to be low at low pH values, and in the presence of K2CO3, which may be useful for surfactant-ionic liquid system regeneration.