The structure and transport properties of a four different films based on two different generations of microfibrillated cellulose (MFC), alone or in combination with glycerol as plasticizer, were investigated through FE-SEM analysis and sorption or permeation experiments. FE-SEM revealed the existence of complex structures in the different samples. A porous, closely packed fiber network, more homogeneous in the samples containing glycerol, was characteristic of the surface of MFC films; while film cross-sections presented a dense layered structure with no evidence of porosity. Water vapor sorption experiments confirmed the hydrophilic character of these cellulosic materials and showed a dual effect of glycerol which reduced the water uptake at low water activity while enhancing it at high relative humidity. The water diffusion in dry samples was remarkably slow for a porous material, confirming the existence of complex structures below the film surface. In contrast, the diffusion coefficient was definitely affected by plasticization, being higher for glycerol-containing samples and showing in all cases an exponential increase when water was added to the system. Similar behavior was observed in permeation experiments. Dry MFC films showed excellent oxygen barrier properties; however, a dramatic decrease in these properties was observed when the water content in the samples was increased. (C) 2010 Elsevier B.V. All rights reserved.