This work focuses on the study of the mass transfer of arsenic(V) through asymmetric polyvinylidene fluoride hollow-fiber membrane contactors using Aliquat-336 as an extractant. In the first part of this work, the fibers were prepared and characterized by SEM and by determining their thickness and porosity. From SEM pictures, an asymmetric structure was obtained that was characterized by an inner sponge-like structure and outer finger-like structure with a pore radius and porosity about 0.11 µm and 80%, respectively. In the second part, the prepared fibers were used as membrane contactors for the study of mass transfer of arsenic(V), investigating the effect of several parameters such as pH, temperature, and initial concentration of the feed. The overall mass transfer coefficient of As(V) was around 6 × 10^–6 cm/s.