The development of more selective chelators for the washing of heavy metal contaminated soil is desirable in order to avoid excessive dissolution of soil minerals. Speciation and mobility of Cu, Zn, Pb, and Ni in a contaminated soil washed with phenyldiaminetetraacetic acid (PDTA), a derivative of EDTA, were investigated by batch leaching test using a range of soil washing conditions followed by sequential extraction. With appropriate washing conditions, PDTA significantly enhanced extraction of Cu from the contaminated soil. The primary mechanisms of Cu extraction by PDTA were complexation-promoted dissolution of soil Cu and increased dissolution of soil organic matter (SOM). PDTA showed high selectivity for Cu(II) over soil component cations (Ca(II), Mg(II), Fe(III), Mn(II), Al(III)), especially at lower liquid-to-soil ratios under PDTA deficiency, thus avoiding unwanted dissolution of soil minerals during the soil washing process which can degrade soil structure and interfere with future land use. PDTA-enhanced soil washing increased the exchangeable fractions of Cu, Zn, and Pb and decreased their residual fractions, compared to their levels in unwashed soil.