Medium- and long-chain triacylglycerols (MLCTs)–enriched structured lipid (SL) was synthesised through enzymatic interesterification from Cinnamomum camphora seed oil (CCSO) and camellia oil (CO) using Lipozyme RM IM from Rhizomucor miehei as a biocatalyst. Effects of different reaction conditions including substrate molar ratio, reaction time and reaction temperature were investigated. Results showed that 55.81% of total MLCT species (CCO/LaCL, LaCO/LCL, COO/OCO and LaOO/OLaO) was obtained in the interesterified product under the optimal conditions of substrate molar ratio of 1:1.5 (CCSO/CO) at 60 °C for 3 h. Thereafter, fatty acid profiles, tocopherol contents and physiochemical characteristics of the interesterified product and physical blend were comparatively investigated. The fatty acid composition of the interesterified product consisted of capric acid (26.33%), lauric acid (21.29%) and oleic acid (42.33%). It should be mentioned that the interesterified product contained predominantly oleic acid (88.69%) at Sn-2 position, while MCFAs (68.05%) at Sn-1,3 positions. Compared with physical blend, the reduction in tocopherol contents and changes of physiochemical characteristics occurred in SL. The smoke point of the interesterified product was much higher than that of the physical blend, which meant that such MLCTs-enriched SL could be better for cooking purpose.