In this Paper, PVC membrane Selective clectrodes are prepared for theophylline which are based on its ion-pair complexes with hexadecylt- rioctylammonium iodide (HTOA) , hexadecyltributyl-ammonium iodide (HTBA), hexadeeyltriophenylphosphonium iodide(HTPP), triphenyloctylphosphonium leoide(TPOP) and tri(p-tolyl) butylphosphonium iodide(TPTBP).The effects of the nature of associate counterions, the plastieizers and their concentrations in the membrane phase have been studied. The electrode based on theophylline-HTOA membrane has a sub-Nernstian response range from 2.0×10~2—6.3×10~(-5)mol/L,with an average slope of 48.0mV/pC. The limit of detection is 8.7×10~(-6)mol/L. The electrode responses were not affected by pH in the range 10-12. The potentiometric selectivity coefficients of various common inorganic and organic ions including those which are similar to theophylline in structure were determined. The Na_2CO_3-Na_2B_4O_7 buffer of pH 11 is selected as the background solution for potentiometric measurements. The electrode was used for determining the theophylline in pharmaceutical preparations with satisfactory results.