The emulsifying characteristics of pectins isolated from six different okra genotypes were investigated and their structure-function relationships have been evaluated. Emulsion formation and stabilization of acidic oil-in-water emulsions (pH 2.0, φ = 0.1) were studied by means of droplet size distribution, ζ-potential measurements, viscometry, interfacial composition analysis and fluorescence microscopy. Fresh and aged emulsions differed in terms of droplet size distribution, interfacial protein and pectin concentrations (Γ) depending on the molecular properties of pectin that was used. Specifically, pectins with intermediate length of RG-I branching with molar ratio of (Ara + Gal)/Rha between 2 and 3 exhibit the optimum emulsification capacity whereas samples with the molar ratio outside this range do not favour emulsification. Additionally, low amounts of RG-I segments (HG/RG-I > 2) improve long term stability of emulsions as opposed to the samples that contain high amounts of RG-I (HG/RG-I < 2) which lead to long term instability. Protein was not found to be the controlling factor for the stability of the dispersions. The present results show that rational design of pectin should be sought before application as functional ingredient in food and/or pharmaceutical systems.