Separation of As(III) and As(V) ions from sulphate media by hollow fiber supported liquid membrane has been examined. Cyanex 923 was diluted in toluene and used as an extractant. Water was used as a stripping solution. The extractability of As(V) was higher than As(III). When the concentration of sulphuric acid in feed solution and Cyanex 923 in liquid membrane increased, more arsenic ions were extracted into liquid membrane and recovered into the stripping solution. The mathematical model was focused on the extraction side of the liquid membrane system. The mass transfer coefficients of the aqueous phase (ki) and organic phase (km) are 7.15×10.3 and 3.45×10.2 cm/s for As(III), and 1.07×10.2 and 1.79×10.2 cm/s for As(V). Therefore, the rate-controlling step for As(III) and As(V) in liquid membrane process is the mass transfer in the aqueous film between the feed solution and liquid membrane. The calculated mass transfer coefficients agree with the experimental results.