An edible film to carry l-(+)-ascorbic acid (AA) was formulated for natural antioxidant food protection. Considering previous works where films based on the "rigid" structure of gellan (deacylated) or on a mixture of acylated-deacylated (more "disordered") gellan were used for network development, pectin was herein chosen by considering that the alternating presence of "disordered" (hairy) regions together with ordered (homogalacturonan) ones could sufficiently immobilize water for better AA retention and lower browning. High methoxyl pectin (HMP) was first investigated. AA stability and browning were studied during film storage at 33.3, 57.7, or 75.2% relative humidity (RH) and 25 degrees C; their dependence on water mobility determined through (1)H NMR analysis as well as the correlation between browning and AA degradation were again found. Network characteristics and glycerol (plasticizer) interactions were analyzed through X-ray diffraction and Fourier transform infrared spectroscopy as well as through uniaxial tensile assay. From all results obtained, it was hypothesized that browning development in solidlike systems may be directly related to the water molecules more closely adsorbed on the hydroxyl-polymeric (active) surfaces. The HMP film microstructure produced the best immobilization of water molecules except at 75.2% RH, where it showed lower AA stability than acylated-deacylated gellan film. It is suggested that disordered regions of this pectin network may not be adequately counterbalanced by more transient junction zones of alternating hydrophilic (water) and hydrophobic (methyl ester) interactions, also disturbed by glycerol molecules, for accomplishing enough water immobilization in the whole network at 75.2% RH.