Non-destructive imaging techniques are essential for characterising spatiotemporal behaviour of polymer-based drug delivery systems, particularly for evaluating in vitro drug distribution and release kinetics. Here, we present a multimodal in situ imaging approach employing confocal Raman microscopy and fluorescence imaging to investigate methacrylate-based photopolymer microstructure polymerised together with PLGA in the blend, while encapsulating dexamethasone fluorescein as a model drug. Raman spectral analysis confirms both polymer and drug components presence within the composite structure, while hyperspectral Raman imaging provides spatial mapping across the 3D microstructure, capturing both areal and depth-resolved heterogeneity. Furthermore, time-dependent fluorescence imaging offers complementary temporal data on drug localisation and diffusion by tracking real-time water penetration and polymer surface degradation. Fluorescence intensity flux serves as a proxy for drug release kinetics and is further validated through quantitative spectrophotometer analysis. By correlating chemical specific information from Raman microscopy with dynamic visualisation from fluorescence imaging, this approach enables comprehensive in situ monitoring of biophysical properties under simulated physiological conditions without compromising the microstructural integrity or disrupting the experimental environment.