The surface enhanced Raman scattering spectroscopy (SERS) is introduced as a new method to probe the initial release of active agents from controlled delivery systems. As a model system, mitoxantrone-loaded polypropylene specimens immersed in water have been utilized. Surface enhanced resonance Raman scattering (SERRS) measurements allowed the quantitative delineation of the initial drug release profile. SERRS was also compared in early stage release processes with UV–vis absorption often used in traditional quantitative analysis via HPLC, a common technique for controlled release evaluation. More and above the high selectivity of the Raman Effect, SERS has been proved as a highly sensitive method to quantitatively monitor the initial release of the medicine even at the very early stage of the delivery process; UV–vis absorbance was unable to respond accordingly. Copyright © 2012 John Wiley & Sons, Ltd.