Molecular mobility of ascorbyl palmitate and α-tocopherol in the presence of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) were determined by NMR relaxation technique. Synergistic effects of DOPC on the antioxidative capacities of ascorbyl palmitate were evaluated in DPPH radical scavenging assay and bulk oil matrix. NMR relaxation technique can provide information on the mobility of protons. Molecular mobility of two protons in hydroxyl group of ascorbyl palmitate decreased by 85 and 78% in the presence of DOPC compared to those without DOPC. However, proton mobility of α-tocopherol increased by 41% when DOPC was present. DOPC significantly enhanced the DPPH reactivity in medium chain triacylglycerol, while this effect was not observed in α-tocopherol. Mixture of ascorbyl palmitate with DOPC showed synergistic antioxidant properties in corn oil at 60 °C. DOPC may make protons of ascorbyl palmitate in more rigid state, which can enhance hydrogen donating ability and antioxidant properties of ascorbyl palmitate in bulk oils.