Multifunctional metallic nanostructures are essential in the architecture of modern technology. However, their characterization remains challenging due to their hybrid nature. In this study, we present a novel photoreduction-based protocol for augmenting the inherent properties of imidazolium-containing ionic polymers (IIP)s through orthogonal functionalization with gold nanoparticles (Au NPs) to produce IIP_Au NPs, as well as novel and advanced characterization via three-dimensional correlation thermal field-flow fractionation (3DCoThFFF). Coordination chemistry is applied to anchor Au3+ onto the nitrogen atom of the imidazolium rings, for subsequent photoreduction to Au NPs using UV irradiation. Thermal field-flow fractionation (ThFFF) and the localized surface plasmon resonance (LSPR) of Au NPs are both dependent on size, shape, and composition, thus synergistically co-opted herein to develop mutual correlation for the advanced analysis of 3D spectral data. With 3DCoThFFF, multiple sizes, shapes, compositions, and their respective distributions are synchronously correlated using time-resolved LSPR, as derived from multiple two-dimensional UV-vis spectra per unit ThFFF retention time. As such, higher resolutions and sensitivities are observed relative to those of regular ThFFF and batch UV-vis. In addition, 3DCoThFFF is shown to be highly suitable for monitoring and evaluating the thermostability and dynamics of the metallic nanostructures through the sequential correlation of UV-vis spectra measured under incremental ThFFF temperature gradients. Comparable sizes are measured for IIP and IIP_Au NPs. However, distinct elution profiles and UV-vis absorbances are recorded, thereby reaffirming the versatility of ThFFF as a robust tool for validating the successful functionalization of IIP with Au to produce IIP_Au NPs.