Pinocembrin is a natural flavonoid compound which is capable of antioxidant, antibacterial, anti-inflammatory, and antineoplastic activities. The present study aimed to enhance the solubility and antioxidant activities of pinocembrin by complex formation with lecithin. The physicochemical characteristics of pinocembrin–lecithin complex were analyzed by ultraviolet (UV), fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and solubility assay, and the antioxidant activities of pinocembrin–lecithin complex were evaluated via radical scavenging capacities for 2,2′-diphenyl-1-picrylhydrazyl (DPPH), 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS), hydroxyl, and superoxide-anion. The results indicated that pinocembrin complex with lecithin could significantly improve the solubility of pinocembrin in water and n-octane, the pinocembrin–lecithin complex displayed no characteristic endothermic peak and the appearance of amorphous state, compared to the pinocembrin, and no new covalent bond was produced in the pinocembrin and lecithin compound. It was demonstrated that the antioxidant activities of pinocembrin were obviously enhanced by the complex with lecithin, and the scavenging capacities for hydroxyl radical, DPPH, superoxide-anion radical, and ABTS radical of pinocembrin–lecithin complex were 82.44 ± 2.21%, 40.07 ± 1.32%, 59.15 ± 0.86%, and 24.73 ± 1.04% at 1.0 mg/mL, respectively. It suggested that the pinocembrin–lecithin complex had a great potential application prospect in the healthcare industry and in clinical practice.