To determine the environmental free metal ion activity was a recent hot issue. A method to measure low-level free cupric ion activity in soil solution extracted with 0.01 mol/L KNO3 was developed by using cupric ion-selective electrode (ISE) and calibrating with Cu-buffer solution. Three copper buffers including iminodiacetic acid (IDA), ethylenediamine (EN), and glycine (Gly)were compared for calibrating the Cu-ISE curves in the range of free cupric ions (pCu2+) 7-13. The Cu-EN buffer showed the best electrode response and thus was applied as the calibration buffer. The pCu2+ of 39 contaminated agricultural soils around a copper mine was measured, ranging from 5.03 to 9.20. Most Cu in the soil solutions was found to be complexed with dissolved soil organic matters, averaging 98.1%. The proportion of free Cu2+ ions in the soil solutions decreased with the increasing of solution pH. Soluble Cu and free Cu2+ ions concentrations were analyzed by multiple linear regressions to evaluate the effects of soil properties on metal levels and speciation. The results showed that soil solution pH was the most significant factor influencing pCu2+ (with R2 value of 0.76), while not important for the soluble Cu concentration.