The use of food biopolymers for structuring edible oil is considered to have huge potential because they are recognized as food ingredients. As most food polymers are hydrophilic in nature, indirect routes (such as emulsion-templates or foam templates and solvent exchange) are employed for liquid oil structuring. For many years, food biopolymers such as proteins and polysaccharides have been investigated to stabilize oil-in-water (O/W) emulsions via biopolymer complexation, which results in a higher stability compared to the use of individual biopolymers. In this chapter, we report the use of O/W emulsions with high oil fractions (HIPE, φ = 0.82) as templates to obtain structured oil systems. The first step involves formation of HIPEs stabilized through adsorption of the biopolymer complexes at the oil–water interface. Subsequently, the water is completely removed (>97 wt% oil) through mild temperature drying to obtain structured oil systems where the mobile oil is entrapped in the structural framework made up of interpolymeric layers of protein–polysaccharide complexes.