Soil samples were collected from apple orchards 5, 15, 20, 30, and 45 years old, and one adjacent forest soil was used as reference to investigate the free Cu(2+)ion activity in soil solution and the soil Cu fractionation in the solid phase following long-term application of copper fungicide, Bordeaux mixture, in apple orchards and to investigate the relationships among soil free Cu(2+)ions, Cu fractionation and soil microbial parameters. The total Cu concentration in the orchard soils varied from 21.8 to 141 mg kg(-1), increasing with the orchard age, and the value for the reference soil was 12.5 mg kg(-1). The free Cu(2+)ion concentrations in the soil solutions extracted by 0.01 mol L(-1) KNO3 ranged from 3.13 x 10(-8)(reference)to 4.08 x 10(-6)mol L(-1)(45 years-old orchard). The concentration of Cu complexed in the fulvic fraction increased with orchard age from 5.16 to 52.5 mg kg(-1). This～also the case for other soil Cu fractions except the residual one. The residual soil Cu remained practically constant, ranging from 4.28 to 5.66 mg kg(-1), suggesting that anthropogenic soil Cu mainly existed in the more labile active fractions. Regression analyses revealed that both the free Cu(2+)ions in the soil solution and the humic acid-complexed Cu fraction in the solid phase were strongly related with soil microbial parameters.