New PVC based polymeric membrane electrodes (PME) and coated glassy carbon electrodes (CGCE) based on synthesized Schiff base complexes of Co(III); [Co(Salen)$(PBu_3)_2$]$ClO_4$, [Co($Me_2$Salen)$(PBu_3)_2$]$ClO_4$, [Co(Salen)$(PBu_3)H_2O$]$ClO_4$; as anion carriers for potentiometric determination of $ClO_4;^-$were studied. The PME and also CGCE electrodes prepared with [Co(Me2Salen)$(PBu_3)_2$]$ClO_4$ showed excellent response characteristics to perchlorate ions. The electrodes exhibited Nernstian responses to $ClO_4;^-$ ions over a wide concentration range with low detection limits ($1.0 { imes} 10^{-6};mol;L^{-1}$ for PME and $9.0 { imes} 10^{-7};mol;L^{-1}$ for CGCE). The electrodes possess fast response time, satisfactory reproducibility, appropriate lifetime and, most importantly, good selectivity toward $ClO_4;^-$ relative to a variety of other common inorganic anions. The potentiometric response of the electrodes is independent of the pH in the pH range 2.5-8.5. The proposed sensors were used in potentiometric determination of perchlorate ions in mineral water and urine samples. The interaction of the ionophore with perchlorate ions was shown by UV/Vis spectroscopy.