We present a novel measurement technique to study an oscillating chemical reaction using a new class of sensor, viz. a pulsating sensor developed in-house. A halogen-free oscillating chemical reaction in the Cu(II)-catalyzed H2O2-KSCN-NaOH system reported by Orban was chosen to examine the performance of this technique. Shift in potential during the oscillating reaction was captured online with high precision and excellent resolution using this simple but high-performance pulsating potentiometric measurement technique. In this work, the influence of bath temperature and flow rate of reagents on the Cu(II)-catalyzed H2O2-KSCN-NaOH oscillating chemical reaction is investigated to optimize the conditions for rapid oscillations. This, in turn, helps to evolve analyte pulse perturbation techniques for rapid assay of hydrazine, uranium(VI), and sodium thiosulfate in aqueous solutions using the above oscillating reaction. © 2012 Wiley Periodicals, Inc.