In this work the mass transfer analysis of the pervaporative separation of chloroform from aqueous solutions in hollow fiber devices has been performed. Experimental results were obtained working at different initial chloroform concentrations (200-1000 mg/l, different flow rate values (0.02-0.105 l/min) and different temperature values (30-50 degrees C). A systematic methodology has been applied to the analysis of the mass transfer rate of the separation process. Thus, starting with kinetic models based on lumped parameters and widely applied in the literature for the description of similar systems, finally a mathematical model resulting from the solution of the continuity equation of the feed phase flowing in laminar regime through the hollow fiber module has been proposed. The diffusivity of chloroform in the aqueous solutions was the only parameter required to describe the separation rate values obtained at different flow rates and different temperatures. Average values of the diffusion coefficient were obtained at each temperature simulated and they were compared to the values predicted by the Wilke-Chang correlation observing similarity. The influence of the temperature was described through the equation D (m(2)/s) = 2.3 x 10(-4) exp(-3738.5/T).