An optimal citric acid extraction condition (pH 2.0; extraction temperature: 120 °C; extraction time: 3 h) was developed to obtain polysaccharide from Laminaria japonica. The yield of polysaccharide was 13.31 ± 0.08%, with IC50 value of DPPH radical scavenging activity of 0.98 ± 0.01 mg mL−1. The viscosity of polysaccharide extracted by citric acid (LJPA) was eight times lower than that of polysaccharide extracted by hot water (LJPW), which may be attributed to the low average molecular weight of LJPA (17.12 kDa). Gas chromatography analysis indicated that LJPA was composed of rhamnose, fucose, xylose, manose, glucose and galactose with relative molar percentages of 4.51%, 20.27%, 12.43%, 12.81%, 10.29% and 39.69% respectively. Furthermore, LJPA exhibited significantly higher antioxidant capacities including oxygen radical absorbance capacity (ORAC), ABTS radical scavenging activity and reducing power than LJPW. Citric acid extraction showed a positive influence on the polysaccharide degradation and antioxidant capacities of L. japonica.