Strain Pseudomonas aeruginosa BC1 was cultured in the fermentation coupling with pervaporation (FCP) system and the fed-batch fermentation system separately for production of rhamnolipids and the two fermentation process each lasted for 124h and 107h respectively. In the FCP system, the maximum optical density OD600 of the biomass was 1.06; maximum optical density OD600 of biosurfactant was 0.61; meanwhile, the total rhamnolipids concentration was quantified as 1.3g/L, which was 38% more than that in the fed-batch fermentation system; in the 29th hour of the FCP process, the surface tension of the fermentation supernatant was 22.56mN/m, as a contrast, the surface tension of pure water was 67.52mN/m. Furthermore, the fermentation supernatant showed excellent emulsifying ability to liquid paraffin, motor oil, diesel oil, n-hexane and hexadecane. The permeation vapor was analyzed by gas chromatography mass spectrometry (GC-MS) coupling with solid-phase micro-extraction (SPME) and several volatile organic compounds were detected, including ethanol, pentanol etc. The data indicate that, in contrast to the fed-batch system, the FCP system can increase the cell concentration and the rhamnolipids production through removing growth inhibition of cells from some volatile metabolites produced in the fermentation process.