In this study, we developed a novel methodology that combines photo-polymerization reaction to fix non-equilibrium colloidal assemblies into permanent structures, combined with high-resolution imaging for detailed structural analysis. While similar techniques, like photopolymerization, optothermal manipulation, and light-triggered assembly, have succeeded in fixing large nanoparticles and small clusters, they face limitations in achieving precise large-scale assemblies and struggle with nanoparticles smaller than the diffraction limit during structural analysis. We present a novel workflow, Fixation and Resolution of colloidal Active Matter Ensembles (FRAME), designed to investigate transient/non-equilibrium colloidal assemblies through a twostep process. First, UV photopolymerization is used to lock the non-equilibrium optical matter (OM) assembly within a hydrogel polymer network, which captures the dynamic snapshot of the OM by immobilizing it permanently. Second, high-resolution imaging techniques such as 3D confocal microscopy and SEM are employed to characterize the position and arrangement of the nanoparticles. We applied FRAME to optical matter structures formed via optical trapping at the interface of colloidal nanoparticles ranging from 200 nm to 1 μm. Validation through confocal and SEM imaging confirmed that the workflow does not alter the structural properties of the assemblies. For particles larger than the diffraction limit, FRAME enables 3D structural analysis, including crystallinity and lattice parameters, while high-resolution SEM resolves assemblies with particles below the diffraction limit. This approach facilitates the characterization of nonequilibrium colloidal assemblies, supporting their design for desired applications.