The experimental design method was used to investigate the PECVD parameters effects on the properties of plasma polysiloxane membranes synthesized using octamethylcyclotetrasiloxane or hexamethyldisiloxane as monomers. On a wide experimental range and with a minimum number of experiments, the use of such a statistical tool enabled us to set up complete and reliable correlations, in the form of polynomial models connecting the gas transport properties (H-2 permeability coefficient, H-2/N-2 ideal selectivity) and the structural properties (growth rate, density, organic/inorganic nature) of synthesized films with the two most influent synthesis parameters of the PECVD process: the input power (represented by the input voltage) and the monomer flux. The polynomial models enabled us not only to statistically confirm the effects of the PECVD parameters displayed by previous classical experimental studies, but also to model, in the mathematical sense, the evolution of each property of materials taking into account the first and second orders effects of both PECVD synthesis parameters. By the use of a performing statistical tool, we managed to improve the knowledge of relations between synthesis parameters/structure/properties relative to our process. (C) 2003 Elsevier B.V. All rights reserved.