In this study, we employ SRS coupled with SFG for the first me for direct in situ nondestruc ve chemicallyspecific imaging of ASD behavior during drug release. Ritonavir (RTV) -polyvinyl pyrrolidone vinyl acetate (PVPVA) amorphous solid dispersion films at different drug-to-polymer ra os served as model systems. Different phenomena, including water penetra on, amorphous-amorphous phase separa on (AAPS), liquid-liquid phase separa on (LLPS), and component release were imaged in real me. Furthermore, the phase separa on was understood through the lens of both surface-directed and bulk phase separa on. (right)) was obtained under the brand name Kollidon® VA 64 from BASF SE (Ludwigshafen, Germany). Methanol (Emsure® for analysis ≥ 99.9 % purity) was supplied by Merck KGaA (Darmstadt, Germany). Phosphate buffer (pH 6.8, 100 mM) was prepared in-house using potassium dihydrogen phosphate (VWR Chemicals BDH®, Leuven, Belgium) and sodium hydroxide (Emsure® for analysis, Merck KGaA, Darmstadt, Germany).