A simple, accurate and highly sensitive spectrophotometric method has been developed for the rapid determination of piroxicam (PX) in pure and pharmaceutical formulations. The proposed method involves formation of stable yellow colored ion-pair complexes of the amino derivative (basic nitrogen) of PX with three sulphonphthalein acid dyes namely; bromocresol green (BCG), bromothymol blue (BTB), bromophenol blue (BPB) in acidic medium. The colored species exhibited absorption maxima at 438, 429 and 432nm with molar absorptivity values of 9.400×103, 1.218×103 and 1.02×104Lmol−1cm−1 for PX–BCG, PX–BTB and PX–BPB complexes, respectively. The effect of optimum conditions via acidity, reagent concentration, time and solvent were studied. The reactions were extremely rapid at room temperature and the absorbance values remained constant for 48h. Beer’s law was obeyed with a good correlation coefficient in the concentration ranges 1–100μgmL−1 for BCG, BTB complexes and 1–95μgmL−1 for BPB complex. The composition ratio of the ion-pair complexes were found to be 1:1 in all cases as established by Job’s method. No interference was observed from common additives and excipients which may be present in the pharmaceutical preparations. The proposed method was successfully applied for the determination of PX in capsule and human blood serum samples with good accuracy and precision.