Antioxidative activities were found in the culture supernatant of Bacillus licheniformis OPL-007 using shrimp head waste (SHW) as the sole carbon and nitrogen source. After optimizing fermentation conditions, some bio-active substances were determined from the broth. The contents of total phenols, polysaccharides, reducing sugars, free amino acids, and organic acids were 888.80, 402.74, 85.88, 2,061.79, and 5,426.74 mg/l, respectively. Moreover, the fermentation liquid was found rich in eight essential amino acids and non-protein amino acids. The antioxidant activity of the culture supernatant, in terms of the scavenging activity of DPPH radicals, reducing power, and metal chelating ability, was monitored, and the fermentation liquid showed a strong antioxidant capacity. The results indicate that bio-deproteinization of SHW by B. licheniformis OPL-007 can increase its antioxidant activity, and SHW has the potential application in the production of functional foods.