Zeta potential and particle size were determined on pectin aqueous solutions as a function of pH andthe effects of calcium ions, putrescine and spermidine on pectin film forming solutions and derived films were studied. Ca2+and polyamines were found to differently influence pectin zeta potential as well as thickness and mechanical and barrier properties of pectin films prepared at pH 7.5 either in the presence or absence of the plasticizer glycerol. In particular, Ca2+was found to increase film tensile strength andelongation at break only in the presence of glycerol and did not affect film thickness and permeability toboth water vapor and CO2. Conversely, increasing polyamine concentrations progressively reduced filmtensile strength and markedly enhanced film thickness, elongation at break and permeability to watervapor and CO2, both in the presence and absence of glycerol. Our findings indicate that polyamines giverise to a structural organization of the heteropolysaccharide different from that determined by calciumions, previously described as “egg box” model, and suggest their possible application as plasticizers toproduce pectin-based “bioplastics” with different features.