For the surficial sediments sampled from the Shaxi River in Sanming, Fujian Province, China, the distribution characteristic of heavy metal copper in surficial sediments were investigated. The microwave digestion result showed that the concentration of Cu in surficial sediments ranged from 26.95 mg/kg to 74.76 mg/kg. The results of modified BCR sequential extraction procedure showed that heavy metal copper in the surficial sediment was mainly associated with residual and reducible fractions. The fractions of copper sampled near the wastewater discharge were in the order of residual > reducible > oxidizable > acid soluble > water soluble fraction, and in the order of residual > reducible > acid soluble > oxidizable > water soluble fraction in samples away from the wastewater discharge. The results indicated that the concentration and fraction of pollutant copper were significantly correlative to the wastewater discharge of some iron and steel factory around the Shaxi River, which varied obviously with the downstream distance increasing to the wastewater discharge. The reducible and oxidizable fractions decreased with the downstream distance increasing to the wastewater discharge of iron and steel factory, however, the acid soluble fraction increased with the distance increasing.