This study aimed to investigate the enzymatic hydrolysis of sunflower, olive, and flaxseed oils and its impact on starch complexation and properties. Enzymatic treatment significantly increased free fatty acid content to 45% without any significant change in fatty acid composition and oxidation precursors. The complexation of high amylose maize starch with hydrolysed flaxseed oil was effective in limiting starch digestion. The highest resistant starch content and expected glycemic index value were determined in starch lipid complex formed by hydrolysed flaxseed oil to be 69.11% and 56.44, respectively. According to XRD patterns, V-type formation was obtained only in complexes formed by hydrolysed oils. Overall, it is concluded that enzymatic hydrolysis of polyunsaturated triglyceride fatty acids to free fatty acids and subsequent complexation with starch can be effective in the production of RS5.